SUPRAMOLECULAR SELECTION IN MOLECULAR AND FRAMEWORK CO-CRYSTALS

Jocelyne Bouzaid

Bachelor of Applied Science Honours I (Chemistry) Bachelor of Business (Management/Marketing)

Submitted in partial fulfilment of the requirements for the degree of

Doctor of Philosophy

School of Chemistry, Physics and Mechanical Engineering Faculty of Science and Engineering Queensland University of Technology 2014 Supramolecular Selection in Molecular and Framework Co-crystals

Keywords

Co-crystal, co-crystallisation, composite crystal, coordination framework, coordination network, coordination polymer, crystal engineering, crystalline solid solution, epitaxial growth crystals, framework alloy, heteromolecular crystal, hybrid materials, metal dilution, metallic doping, metal-organic framework, metal-organic network, mixed crystal, mixed-metal compounds, molecular alloy, molecular complex, molecular composite, molecular recognition, multicomponent crystal, supramolecular alloy, supramolecular chemistry, supramolecular motif, supramolecular selection.

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Supramolecular Selection in Molecular and Framework Co-crystals

Abstract

One of the ongoing challenges in supramolecular chemistry and crystal engineering is the development of methods for synthesising multifunctional crystalline materials that have predictable structural architectures and tunable solid-state properties. One strategy is through the exploitation of known supramolecular motifs and architectures to engineer molecular and framework co-crystals, which are essentially solid solutions of molecules in the crystalline state. In this project, single co-crystals were formed by the co-crystallisation of metal complexes that have similar molecular and crystal structures but different physical or chemical properties.

II 2+ II By co-crystallising [M (terpyR)2] (M = Fe, Co, Ni, Cu; 2+ terpy = 2,2′:6′,2′′-terpyridine; R = H, OH) with [Ru(terpy)2] it was possible to II exploit the 2D terpy embrace motif to synthesise four [M xRu1-x(terpy)2](PF6)2 II II II (M = Fe, Co, Ni, Cu) and five [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (M = Fe, Ni, Cu) novel co-crystals. Co-crystals were characterised using XRD and SEM-EDX, the latter to quantify the amount of each metal complex present in single co-crystals. SEM-EDX results indicated that co-crystals grown from the same solution were found to have a range of concentrations such that xsolid single crystal 1 ≠ xsolid single crystal 2.

The variation in the relative metal complex concentration among single co-crystals grown from the same solution is indicative of molecular recognition for like complexes resulting in supramolecular selection. It appears that for systems that display supramolecular selection, intermolecular interactions between like complex pairs are more energetically favoured than interactions between different complexes but not enough to result in exclusive crystallisation.

In addition, several novel framework co-crystals and crystals exhibiting epitaxial III 3- growth were prepared using [M (ox)3] metal complexes as molecular building- blocks (MIII = Cr, Fe; ox = oxalate). Co-crystals, with the formula

K3[CrxFe1-x(ox)3]·2.5H2O were analysed using single crystal surface and confocal Raman spectroscopic mapping, SEM-EDX and PXRD and were found to exhibit directional intracrystal concentration gradients. The presence of a concentration gradient is remarkable and presents the potential for a single crystal to display an ii

Supramolecular Selection in Molecular and Framework Co-crystals infinitely varying degree of magnetism as well as other concentration dependent properties.

A total of five crystals exhibiting epitaxial crystal growth were also prepared from III III K3[M (ox)3]·2.5H2O (M = Cr and/or Fe) seed crystals that were immersed into III III saturated solutions of K3[M (ox)3] (M = Cr, Fe or a 1:1 mixture). Different epitaxial growth patterns were observed depending on the method used to immerse the seed crystals into the solution. Experiments also indicated that supramolecular interactions between like and different complexes are similar enough to allow simultaneous growth to occur on both types of crystals but that interactions between like complexes are slightly more favourable.

II III Lastly, four different [M (L)3][NaM (ox)3] co-crystals were prepared by II II co-crystallising [M (L)3]Cl2 (M = Ni, Ru; L = 2,2′-bipyridine (bipy), III III 1,10-phenanthroline (phen)) with K3[M (ox)3] (M = Cr, Fe) in the presence of NaCl. Co-crystals were characterised using SEM-EDX, SCXRD and PXRD.

[Ni0.50Ru0.50(bipy)3][NaCr(ox)3] co-crystals were found to have the same ratio of the II 2+ metal complexes that was present in solution indicating that [M (bipy)3] complexes engage in negligible supramolecular selection during co-crystallisation. Results obtained from [Ru(bipy)3][NaCr0.60Fe0.40(ox)3] co-crystals suggest that K3[Cr(ox)3] was slightly favoured over K3[Fe(ox)3]. [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] and

[Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] co-crystals were found to have a II 2+ II 2+ [M (bipy)3] : [M (phen)3] ratio of 4:1.

Co-crystals of all four of these coordination frameworks were found to be II 2+ isomorphous. Most interestingly, it was discovered that the [M (phen)3] molecules A B in both [M (bipy)3]0.80[M (phen)3]0.20[NaCr(ox)3] structures exhibited the opposite II 2+ 2- chirality to the [M (bipy)3] complexes and to the metals in the {[NaCr(ox)3] }n helical anionic framework such that single co-crystals had the general formula A B Λ-[M (bipy)3]0.80Δ-[M (phen)3]0.20Λ-[NaCr(ox)3]. The heterochiral structure of II III these co-crystals is especially novel as [M (L)3][NaM (ox)3] single crystals have historically been known to only form homochiral structures.

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Supramolecular Selection in Molecular and Framework Co-crystals

Table of Contents Keywords ...... i Abstract ...... ii Table of Contents ...... iv List of Figures ...... viii List of Tables ...... xiv List of Abbreviations ...... xvi Statement of Original Authorship ...... xviii Acknowledgements ...... xix Quotation ...... xxi

CHAPTER 1: Introduction ...... 1

1.1 Supramolecular chemistry ...... 1

1.2 Crystal engineering ...... 2

1.3 Intermolecular interactions ...... 5

1.4 Supramolecular motifs ...... 12

1.5 Lattice dimensionality ...... 14

1.6 Multicomponent crystals ...... 15

1.6.1 Nomenclature ...... 15

1.6.2 Co-crystal systems in the literature ...... 17

1.6.3 The discovery of supramolecular selection ...... 25

CHAPTER 2: Project objectives ...... 35

2.1 Overall research objectives ...... 35

2.2 Molecular co-crystalline materials ...... 36

2.3 Metal-organic framework co-crystalline materials ...... 38

CHAPTER 3: Preparative experimental details and methodology ...... 40

3.1 Materials ...... 40

3.2 Characterisation techniques ...... 40

3.2.1 Scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) ...... 40

3.2.2 Powder X-ray diffraction (PXRD) ...... 41 iv

Supramolecular Selection in Molecular and Framework Co-crystals

3.2.3 Single crystal X-ray diffraction (SCXRD) ...... 42

3.2.4 Nuclear magnetic resonance spectroscopy (NMR) ...... 43

3.2.5 High resolution electrospray ionisation mass spectrometry (ESI-MS) ...... 43

3.2.6 Raman spectroscopy ...... 43

3.2.7 Elemental analysis ...... 44

3.3 Synthetic experimental details ...... 45

3.3.1 Synthesis of 4′-phenyl-2,2′:6′,2′′-terpyridine (terpyPh) ...... 45

II 3.3.2 Synthesis of [M (L)2]X2 transition metal complexes ...... 47

II 3.3.3 Synthesis of [M (L)3]X2 transition metal complexes ...... 56

III 3.3.4 Synthesis of K3[M (ox)3]·xH2O complexes ...... 59

3.3.5 Binary co-crystallisation experiments ...... 63

3.3.6 K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O epitaxial experiments ...... 67

II III 3.3.7 Synthesis of [M (L)3][NaM (ox)3] co-ordination metal-organic frameworks ...... 68

II 2+ CHAPTER 4: Co-crystallisation systems incorporating [M (terpyR)2] ..... 70

II 4.1 Background: The [M (terpyR)2]X2 metal complexes and the terpy motif ...... 70

A B 4.2 Background: Previous research into the co-crystallisation of [M (L)n]X2 with [M (L)n]X2

A B to form [M xM 1-x(L)n]X2 co-crystals...... 76

4.3 Results and discussion ...... 80

II 4.3.1 [M xRu1-x(terpy)2](PF6)2 co-crystallisation systems ...... 81

II 4.3.2 [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystallisation systems ...... 99

II 4.3.3 Co-crystallisation experiments involving [M (terpyPh)2](PF6)2, [Ni(phen)3](PF6)2,

[Ni(bipy)3](PF6)2 ...... 118

4.4 Chapter summary and conclusions ...... 120

III 3- CHAPTER 5: Co-crystallisation systems incorporating [M (ox)3] to form framework materials ...... 122

5.1 Background and introduction ...... 122

III 3- 5.1.1 The oxalato ligand (ox) and coordination frameworks containing [M (ox)3] complexes as building-blocks ...... 122

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Supramolecular Selection in Molecular and Framework Co-crystals

5.2 Results and discussion ...... 127

A B 5.2.1 Co-ordination frameworks of the type K3[M xM 1-x(ox)3] ...... 129

II I III 5.2.2 Co-ordination frameworks of the type [M (L)3][M M (ox)3] ...... 158

5.2.3 [NixRu1-x(bipy)3][NaCr(ox)3] (system 1) ...... 170

5.2.4 [Ru(bipy)3][NaCrxFe1-x(ox)3] (system 2) ...... 179

II 2+ 5.2.5 Homoleptic cationic and anionic metal dilutions involving [M (phen)3] and III 3- [M (ox)3] (systems 3 and 4) ...... 183

5.2.6 [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] (system 5) and

[Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3] (system 6) ...... 190

5.3 Chapter summary and conclusions ...... 201

CHAPTER 6: Project summary and conclusions ...... 202

6.1 Overall project summary and conclusions ...... 202

6.2 Novel molecular co-crystals formed through the use of the 2D terpy motif ...... 203

III 6.3 Co-crystallisations using the K3[M (ox)3] metal complex building-block to form novel co-crystalline metal-organic frameworks...... 206

CHAPTER 7: Directions for future research ...... 214

REFERENCES

In text references ...... 216

CSD reference code references ...... 234

APPENDICES

APPENDIX A: The use of SEM-EDX for quantitative analysis ...... 241

APPENDIX B: EDX analysis of the residues obtained by the evaporation of the mother liquors for

II 2+ III 3- co-crystallisation experiments involving [M (L)3] and [M (ox)3] ...... 246

APPENDIX C: PXRD of K3[CrxFe1-x(ox)3]·2.5H2O co-crystals ...... 251

APPENDIX D: Literature SCXRD refinement data for [Fe(terpyOH)2](BF4)2·H2O,

[Cu(terpyOH)2](BF4)2·H2O (CAPXUN, CAPYIC) and experimental data for

[Ni(terpyOH)2](BF4)2·H2O and [Ru(terpy)2](BF4)2·H2O ...... 252

II II APPENDIX E: SCXRD refinement data for [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2·H2O (M = Fe, Ni, Cu) co-crystals ...... 253 vi

Supramolecular Selection in Molecular and Framework Co-crystals

APPENDIX F: Additional SCXRD refinement data for co-crystals of

[Ni0.50Ru0.50(bipy)3][NaCr(ox)3], [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] and

[Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] ...... 254

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List of Figures

Figure 1: Sodium chloride cubic lattice system...... 6 + Figure 2: Octahedral labile [Na(H2O)6] complex ...... 6 z+ Figure 3: [M(bipy)3] complex (bipy = 2,2′-bipyridine) showing coordinate bonds between the metal cation and the nitrogen atom of the ligands...... 7 Figure 4: Geometric arrangement for FF (a) and OFF (b) interactions of the benzene dimer...... 10 Figure 5: Geometric arrangement for EF (a) and VF (b) interactions of the benzene dimer ...... 11 + Figure 6: Primary multiple aryl embrace motifs for Ph4P cations ...... 12 z+ z+ Figure 7: Multiple aryl embraces between pairs of [M(terpy)2] complexes (a) [M(phen)3] z+ complexes (b) and [M(bipy)3] complexes (c) ...... 13 Figure 8: Schematic representations of (a) 1D linear chain, (b) grid (bottom) and honeycomb (top) 2D lattices and (c) matrix (bottom), diamondoid (middle) and extended (top) 3D networks...... 15 Figure 9: 2,6-bis(pyrazol-3-yl)pyridine (bpp) ...... 20 Figure 10: (left to right) 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) and 2,2′;6′,2′′-terpyridine (terpy) ...... 20 A B Figure 11: Photographs of (imidazolium)2[M xM 1-x(dipic)2]·2H2O co-crystals with the metals and their respective ratios given under each image ...... 22 Figure 12: Photographs of slices of G-1 (a, b), G-2 (c, d) and G-3 (e, f) epitaxial growth crystals clearly showing the different Ru containing domains (colourless) and Fe-containing domains (yellow/orange) ...... 24

Figure 13: Microscope images of single crystals of [Ni(phen)3](PF6)20.5H2O,

[Ru(phen)3](PF6)20.5H2O and single co-crystals of [NixRu1-x(phen)3](PF6)20.5H2O obtained by co-crystallisation of an equimolar mixture of the two pure complexes...... 27 Figure 14: Representative ESI mass spectrum obtained for a single co-crystal produced from a solution containing an equimolar mixture of [Ni(phen)3](PF6)2 and [Ru(phen)3](PF6)2 ...... 28

Figure 15: Powder XRD patterns of pure [Fe(L)3](PF6)2 (red), [Ru(L)3](PF6)2 (blue), and

[Ni(L)3](PF6)2 (green) interspersed with the PXRD patterns for respective co-crystals obtained from solutions containing 80:20, 50:50, and 20:80 molar ratios of the metal complexes for systems of A B A B [M xM 1-x(phen)3](PF6)20.5H2O (left) and [M xM 1-x(bipy)3](PF6)2 (right)...... 29

Figure 16: Scatter plot and regression line for SEM-EDX analyses of [NixRu1-x(phen)3](PF6)20.5H2O co-crystals...... 30

Figure 17: Scatter plot and regression line for SEM-EDX analyses of [NixRu1-x(bipy)3](PF6)2 co-crystals...... 32 Figure 18: 4′-Phenyl-2,2′:6′,2′′-terpyridine (terpyPh) ...... 46 Figure 19: Schematic describing co-crystallisation experiments of complexes A and B via vapour diffusion of ethanol into water...... 65 Figure 20: The structure of 2,2′:6′,2′′-terpyridine (terpy) showing the atom numbering of each pyridyl ring...... 70 II 2+ Figure 21: The orthogonal arrangement of the terpy ligands of typical [M (terpy)2] cations as viewed perpendicular to the S4 axis (left) and along the S4 axis (right) ...... 71 viii

Supramolecular Selection in Molecular and Framework Co-crystals

II 2+ Figure 22: The terpy embrace motif between a pair of [M (terpy)2] complexes...... 72 II 2+ Figure 23: Ball and stick representation showing the interactions between four [M (terpy)2] complexes leading to the structure called the two-dimensional (2D) terpy embrace ...... 72 Figure 24: Space-filled representation of an expanded 2D terpy embrace layer containing nine II 2+ [M (terpy)2] complexes as viewed from the top (left), side (centre) and bottom (right) ...... 73 Figure 25: Plot of EDX results from previous experiments conducted by members of the McMurtrie group of [NixCu1-x(terpy)2](PF6)2 where xsolution = 0.10 to 0.90 in 0.10 increments...... 78 Figure 26: SEM secondary electron image of co-crystals with the general formula

[CoxRu1-x(terpy)2](PF6)2...... 83

Figure 27: EDX spectrum from the area outlined in red on the [CoxRu1-x(terpy)2](PF6)2 co-crystal shown in Figure 26. This co-crystal was found to contain 52% [Co(terpy)2](PF6)2 and 48%

[Ru(terpy)2](PF6)2...... 83 Figure 28: Colour-coded plot of EDX results of co-crystals of the general formula II [M xRu1-x(terpy)2](PF6)2...... 85 z+ Figure 29: A three-dimensional illustration of a [M(terpyR)2] complex showing the orthogonal relationship between the two ligands and the interpreted width and height of the complex...... 87 2+ Figure 30: Width and Height of various [M(terpyR)2] complexes reported in the CSD...... 88 II Figure 31: Powder XRD patterns of freshly prepared pure [M (terpy)2](PF6)2 crystals ...... 91

Figure 32: Powder XRD patterns of freshly prepared [FexRu1-x(terpy)2](PF6)2 co-crystals (shown in purple) with the diffraction patterns of [Fe(terpy)2](PF6)2 (top) and [Ru(terpy)2](PF6)2 (bottom)...... 94

Figure 33: Powder XRD patterns of freshly prepared [CoxRu1-x(terpy)2](PF6)2 co-crystals (shown in blue) with the diffraction patterns of [Co(terpy)2](PF6)2 (top) and [Ru(terpy)2](PF6)2 (bottom)...... 95

Figure 34: Powder XRD patterns of freshly prepared [NixRu1-x(terpy)2](PF6)2 co-crystals (shown in green) with the diffraction patterns of [Ni(terpy)2](PF6)2 (top) and [Ru(terpy)2](PF6)2 (bottom)...... 96

Figure 35: Powder XRD patterns of freshly prepared [CoxRu1-x(terpy)2](PF6)2 co-crystals (shown in blue) and [NixRu1-x(terpy)2](PF6)2 co-crystals (shown in green)...... 97

Figure 36: Powder XRD patterns of freshly prepared [CuxRu1-x(terpy)2](PF6)2 co-crystals (shown in red) with the diffraction patterns of [Cu(terpy)2](PF6)2 (top) and [Ru(terpy)2](PF6)2 (bottom) ...... 98 Figure 37: Secondary electron SEM images of co-crystals with the formula

[Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (left) and [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (right)...... 101 Figure 38: Secondary electron (left) and backscattered (right) SEM images of a co-crystal with the formula [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2...... 101 Figure 39: SEM image of crystals grown from a solution containing a 1:1 ratio of III [Co (terpyO)(terpyOH)](BF4)2 and [Ru(terpy)2](BF4)2 ...... 102 Figure 40: Colour-coded plot of EDX results of co-crystals of the general formula II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 ...... 104

Figure 41: Powder XRD patterns of freshly prepared pure [Ru(terpy)2](BF4)2 and II [M (terpyOH)2](BF4)2 ...... 108

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Supramolecular Selection in Molecular and Framework Co-crystals

Figure 42: Powder XRD patterns of freshly prepared [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals

(purple) shown with the diffraction patterns of [Fe(terpyOH)2](BF4)2 (black) and [Ru(terpy)2](BF4)2

(black). A pattern simulated from the SCXRD structure of [Fe(terpyOH)2]0.60[Ru(terpy)2]0.40(BF4)2 (grey) is shown at the very top of the figure and was used to assign Miller indices to the like patterns shown...... 110

Figure 43: Powder XRD patterns of freshly prepared [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals

(green) shown with the diffraction patterns of [Ni(terpyOH)2](BF4)2 (black) and [Ru(terpy)2](BF4)2

(black). A pattern simulated from the SCXRD structure of [Ni(terpyOH)2]0.60[Ru(terpy)2]0.40(BF4)2 (grey) is shown at the very top of the figure and was used to assign Miller indices to the like patterns shown...... 111

Figure 44: Powder XRD patterns of freshly prepared [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals

(red) shown with the diffraction patterns of [Cu(terpyOH)2](BF4)2 (black) and [Ru(terpy)2](BF4)2

(black). A pattern simulated from the SCXRD structure of [Cu(terpyOH)2]0.50[Ru(terpy)2]0.50(BF4)2 (grey) is shown at the very top of the figure and was used to assign Miller indices to the like patterns shown...... 112 Figure 45: Colour-coded plot of EDX results of co-crystals of the general formula II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 that were grown from solutions containing 5% II [M (terpyOH)2](BF4)2...... 115

Figure 46: Powder XRD patterns of freshly prepared [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (purple)

[Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals (red) that were grown from solutions containing 5% II [M (terpyOH)2](BF4)2. The [Ru(terpy)2](BF4)2 diffraction pattern is also shown (black)...... 117

Figure 47: Powder XRD pattern of freshly prepared [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (green) co-crystals that were grown from a solution containing 5% [Ni(terpyOH)2](BF4)2. Diffraction patterns of [Ni(terpyOH)2](BF4)2 and [Ru(terpy)2](BF4)2 are also shown (black)...... 117 Figure 48: The structure of oxalate (a), 2,2′-bipyridine (b) and 1,10-phanathroline (c)...... 122 z- z- Figure 49: Schematic views showing the propeller-like geometry of Δ-[M(ox)3] and Λ-[M(ox)3] enantiomers...... 123 Figure 50: A schematic representation of the heterochiral arrangement of neighbouring metal centres z- of [M(ox)3] complexes leading to the formation of a 2D (6,3) hexagonal anionic framework...... 124 Figure 51: A schematic representation of the homochiral arrangement of neighbouring metal centres z- of [M(ox)3] complexes with Δ chirality leading to the formation of a 3D (10,3) helical anionic framework...... 125 2- Figure 52: [100] projection of the anionic Δ-{[LiCr(ox)3] }n host framework (left) and the cationic 2+ Δ-[Ru(bipy)3] guests (right) for the Δ-[Ru(bipy)3][LiCr(ox)3] structure reported by Andrés et al. . 126 III Figure 53: PXRD patterns of pure and recrystallised K3[M (ox)3]·xH2O ...... 130 Figure 54: SEM secondary electron image showing crystal aggregation and the various crystal habits resulting from the equimolar co-crystallisation between K3[Fe(ox)3] and K3[Rh(ox)3]...... 133

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Supramolecular Selection in Molecular and Framework Co-crystals

Figure 55: Microscope images showing the crystal habits and colours of pure K3[Cr(ox)3]·2.5H2O

(a), K3[Fe(ox)3]·2.5H2O single crystals (b) and single co-crystals of the formula

K3[CrxFe1-x(ox)3]·2.5H2O (c), which were grown from a solution containing a 1:1 ratio of K3[Cr(ox)3] and K3[Fe(ox)3] ...... 134 Figure 56: SEM image of a co-crystal grown from a solution containing an equimolar ratio of

K3[Cr(ox)3] and K3[Fe(ox)3] ...... 136 Figure 57: Raman spectra highlighting the separation of the carbonyl stretching bands of -1 K3[Fe(ox)3]·2.5H2O and K3[Cr(ox)3]·2.5H2O at 1722.97 and 1727.47 cm respectively ...... 139 Figure 58: Microscope image of a single co-crystal exhibiting a concentration gradient that was co-crystallised from a solution containing an equimolar ratio of K3[Cr(ox)3] to K3[Fe(ox)3] ...... 141 Figure 59: Plot of the Raman peak position across the transect on a single co-crystal that was grown from a solution containing a 1:1 ratio of K3[Cr(ox)3] to K3[Fe(ox)3]...... 142 Figure 60: Plot of the EDX measurements across the transect on a single co-crystal that was grown from a solution containing a 1:1 ratio of K3[Cr(ox)3] to K3[Fe(ox)3]...... 142 Figure 61: Graphical representations of the data derived from a Raman area map conducted on the surface of a single co-crystal that was grown from a solution containing a 1:1 ratio of K3[Cr(ox)3] to

K3[Fe(ox)3]...... 144 Figure 62: A plot of the depth versus the change in the confocal Raman peak position measured along a transect with a tranjectory parallel to the largest facet of a single co-crystal that exhibited a surface concentration gradient and was grown from a solution containing a 1:1 ratio of K3[Cr(ox)3] to

K3[Fe(ox)3] ...... 146 Figure 63: A plot of the depth versus the change in the confocal Raman peak position acquired from two depth-profile maps each from a different single co-crystal (grown from a 1:1 solution of

K3[Cr(ox)3] to K3[Fe(ox)3]). A perpandicular trajectory (relative to the largest facet) was followed by both transects ...... 147 Figure 64: Optical microscope images of one epitaxial crystal grown by immersing a

K3[Fe(ox)3]·2.5H2O seed into a saturated solution of K3[Cr(ox)3](aq/EtOH)...... 150 Figure 65: Optical microscope images of one epitaxial crystal grown by immersing a

K3[Cr(ox)3]·2.5H2O seed into a saturated solution of K3[Fe(ox)3](aq/EtOH)...... 150 Figure 66: The Raman peak positions across a transect from an epitaxial crystal grown by immersing a K3[Fe(ox)3]·2.5H2O seed into a solution of K3[Cr(ox)3](aq/EtOH)...... 152 Figure 67: The Raman peak positions across a transect from an epitaxial crystal grown by immersing a K3[Cr(ox)3]·2.5H2O seed into a solution of K3[Fe(ox)3](aq/EtOH)...... 152

Figure 68: Images of a K3[Cr(ox)3]·2.5H2O seed suspended by a glass fibre in a solution containing

K3[Fe(ox)3](aq/EtOH) before (a) and after (b) epitaxial growth. The image on the right (c) is of an epitaxial crystal resulting from a K3[Fe(ox)3]·2.5H2O seed suspended by a glass fibre in a solution containing K3[Cr(ox)3](aq/EtOH)...... 154

Figure 69: Seed crystals of K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O suspended by glass fibres and immersed in a solution of K3[Fe(ox)3](aq/EtOH)...... 155

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Supramolecular Selection in Molecular and Framework Co-crystals

Figure 70: Optical microscope images of an epitaxial crystal grown by immersing a

K3[Fe(ox)3]·2.5H2O seed into a saturated solution containing an equimolar ratio of K3[Cr(ox)3] and

K3[Fe(ox)3] ...... 156 Figure 71: Plot of the Raman peak position across a transect on a crystal grown from a

K3[Fe(ox)3]·2.5H2O seed immersed in a solution containing an equimolar ratio of K3[Cr(ox)3]and

K3[Fe(ox)3]...... 157

Figure 72: [100] projection of Δ-[Ru(bipy)3][NaCr(ox)3] reported for the 2010 structure by Hauser et al...... 161

Figure 73: (a) Single co-crystals of the general formula [NixRu1-x(bipy)3][NaCr(ox)3] resulting from 2+ 2+ 3- the co-crystallisation of a 1:1:2 ratio of [Ni(bipy)3] , [Ru(bipy)3] and [Cr(ox)3] in the presence of NaCl (system 1), (b) single co-crystal resulting from the co-crystallisation of a 1:1:2 ratio of 2+ 2+ 3- [Ni(phen)3] , [Ru(phen)3] and [Cr(ox)3] in the presence of NaCl (system 3) and (c) a single co-crystal of the general formula [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] resulting from the 2+ 2+ 3- co-crystallisation of a 1:1:2 ratio of [Ni(bipy)3] , [Ruphen)3] and [Cr(ox)3] in the presence of NaCl (system 5)...... 164 Figure 74: EDX plot showing the metal ratio of interest (Ni:Ru or Cr:Fe) and experiment system on the x axis against the xsolid of Ni or Cr on the left and right y axes respectively ...... 166 Figure 75: PXRD patterns of co-crystals from systems 1, 2, 5, 6 that were collected at room temperature indexed against a simulated powder pattern collected from a

[Ni0.50Ru0.50(bipy)3][NaCr(ox)3] single co-crystal at 173K...... 169

Figure 76: SEM image of intertwined mass of crystalline [NixRu1-x(bipy)3][NaCr(ox)3] co-crystals (system 1) ...... 171

Figure 77: SEM image of a representative [NixRu1-x(bipy)3][NaCr(ox)3] single co-crystal resulting 2+ 2+ 3- from the co-crystallisation of a 1:1:2 ratio of [Ni(bipy)3] , [Ru(bipy)3] and [Cr(ox)3] in the presence of NaCl (system 1)...... 172

Figure 78: EDX spectrum from a tetrahedral co-crystal of [Ni0.49Ru0.51(bipy)3][NaCr(ox)3] ...... 173 2- 2+ Figure 79: [100] projection of {Δ-[NaCr(ox)3] }n (left) and Δ-[Ni0.50Ru0.50(bipy)3] (right) for the

Δ-[Ni0.50Ru0.50(bipy)3][NaCr(ox)3] compound...... 177 Figure 80: Diagram illustrating the twist angle (Φ) and s and h parameters used to assess distortion of octahedral complexes...... 177

Figure 81: SEM image of crystalline [Ru(bipy)3][NaCrxFe1-x(ox)3] (system 2)...... 180

Figure 82: EDX spectrum from a tetrahedral [Ru(bipy)3][NaCr0.59Fe0.41(ox)3] co-crystal ...... 181 Figure 83: SEM image of a single co-crystal formed by the co-crystallisation of a 1:1:2 ratio of 2+ 2+ 3- [Ni(phen)3] , [Ru(phen)3] and [Cr(ox)3] in the presence of NaCl (system 3)...... 185 Figure 84: EDX spectra collected from rectangular prism shaped crystals grown from solutions II 2+ III 3- containing [M (phen)3] and [M (ox)3] in the presence of NaCl (systems 3 and 4) ...... 186 Figure 85: SEM images of co-crystals exhibiting penetrative twinning that were grown from a solution containing an equimolar mixture of [Ru(bipy)3](PF6)2 and [Ni(phen)3](PF6)2 detected using secondary electrons (a and b) and backscattered electrons (c and d)...... 191

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Figure 86: EDX spectra measured from crystals grown from co-crystallisation types 5 (a) and 6 (b) with the formula [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] and

[Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] respectively...... 192 2+ 2+ Figure 87: The Λ-[Ru(bipy)3] and Δ-[Ni(phen)3] complexes in

[Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] as viewed along the [100] plane (left) and a perspective that shows all of the ligands associated with the Ni/Ru site (right)...... 197 2+ 2+ Figure 88: Three adjacent Λ-[Ru(bipy)3] and Δ-[Ni(phen)3] complexes in

[Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] as viewed along the [100] axis (left) and a perspective that shows the overlap of the 1,10-phenanthroline carbon atoms (right)...... 198

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List of Tables

Table 1: Calculated hydrogen bond dissociation energy for selected hydrogen bonding interactions in the gas phase...... 8 Table 2: Energetic and geometric properties of strong, moderate and weak hydrogen bond interactions according to Jeffery, 1997...... 9 Table 3: Compound index ...... 45 II 2+ 2+ Table 4: Summary of [M (L)2] and [Ru(L)2] binary co-crystallisation experiments...... 64 2+ 2+ Table 5: Summary of [Ni(L)3] and [Ru(L′)2] binary co-crystallisation experiments...... 65 III 3- III 3- Table 6: Summary of [M (ox)3] and [M (ox)3] co-crystallisation experiments...... 67 III Table 7: Summary of the composition of the K3[M (ox)3]·2.5H2O seed crystals and the III K3[M (ox)3](aq/EtOH) saturated solutions used to crystallise epitaxial growth crystals...... 68 II 2+ III 3- Table 8: Summary of co-crystallisation experiments between [M (L)3] and [M (ox)3] ...... 69 II 2+ Table 9: Summary of crystal structures (in chronological order of publication) of [M (terpy)2] , and II 2+ [M (terpyOH)2] complexes...... 75 II Table 10: Summary of co-crystallisation experiments between [M (terpy)2](PF6)2 and

[Ru(terpy)2](PF6)2 ...... 82

Table 11: Statistical summary of xsolid values obtained from EDX data for experiments resulting in II co-crystals with the general formula [M xRu1-x(terpy)2](PF6)2...... 84 Table 12: Comparison of factors that are known to influence metal complex size and shape...... 89 II Table 13: Summary of co-crystallisation experiments between [M (terpyOH)2](BF4)2 and

[Ru(terpy)2](BF4)2 ...... 100

Table 14: Statistical summary of xsolid values obtained from EDX data for experiments resulting in II co-crystals with the general formula [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 that were formed from II solutions containing 50% [M (terpyOH)2](BF4)2...... 102

Table 15: Statistical summary of xsolid values obtained from EDX data for experiments resulting in II co-crystals with the general formula [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 that were formed from II solutions containing 5% [M (terpyOH)2](BF4)2...... 115 II Table 16: Summary of co-crystallisation experiments between [M (terpyPh)2](PF6)2 and

[Ru(terpy)2](PF6)2; [Ni(L)3](PF6)2 and [Ru(terpy)2](PF6)2 or [Ru(terpyPh)2](PF6)2...... 119 III 3- III 3- Table 17: Summary of co-crystallisation experiments between [M (ox)3] and [M (ox)3] ...... 132 III Table 18: Summary of the composition of the K3[M (ox)3]·2.5H2O seed crystals and the III K3[M (ox)3](aq/EtOH) saturated solutions used to crystallise epitaxial growth crystals...... 149 Table 19: Summary of crystal structures (in chronological order of publication) and crystallising II/III z+ I III 2- conditions of 3D coordination frameworks involving [M (L)3] with either {[M M (ox)3] }n, II III - II 2- I III 2- {[M M (ox)3] }n, {[M 2(ox)3] }n or {[M M (dto)3] }n...... 159 II 2+ III 3- Table 20: Summary of co-crystallisation experiments between [M (L)3] and [M (ox)3] ...... 163

Table 21: Statistical summary of xsolid values obtained from EDX data for experiments 1-6 that II 2+ III 3- involved [M (L)3] and [M (ox)3] complexes ...... 165

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Table 22: Summary of crystal and refinement data for structures of [Ni0.50Ru0.50(bipy)3][NaCr(ox)3],

[Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] and [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3]...... 168

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List of Abbreviations

δ Partial charge Δ Delta (right-handed propeller twist) Λ Lambda (left-handed propeller twist) 1D One dimensional 2D Two-dimensional 3D Three-dimensional 6AE 6-fold Aryl Embrace AAS Atomic Absorption Spectroscopy aq aqueous At% Atomic percent bipy 2,2′-bipyridine CSD Cambridge Structural Database DCM Dichloromethane DMF N,N-dimethylformamide DMSO Dimethyl sulfoxide EDX Energy Dispersive X-ray EF Edge-to-Face ESI-MS Electrospray Ionisation Mass Spectrometry

Et2O Diethyl ether EtOH Ethanol FF Face-to-Face FWHM Full Width at Half Maximum H-bond Hydrogen bond HR High Resolution ICP-MS Inductively Coupled Plasma Mass Spectrometry m/z mass-to-charge ratio

Me2CO Acetone MeCN Acetonitrile MeOH Methanol + NBu4 Tetra-n-butylammonium NMR Nuclear Magnetic Resonance xvi

Supramolecular Selection in Molecular and Framework Co-crystals

. δH (proton chemical shift) 3 . JHH (vicinal proton-proton coupling constant) 4 . JHH (proton-proton coupling constant over 4 bonds) . s (singlet), d (doublet), t (triplet), dd (doublet of doublets), dt (doublet of triplets), td (triplets of doublets), tt (triplets of triplets), ddd (doublet of doublets of doublets) nPrOH n-Propanol O4AE Orthogonal 4-fold Aryl Embrace OFF Offset-Face-to-Face ox oxalate P4AE Parallel 4-fold Aryl Embrace Ph Phenyl phen 1,10-phenanthroline PXRD Powder X-ray Diffraction Refcode CSD crystal structure reference code s(xsolid) Sample standard deviation of molar fraction in solid S.D. Solvent Diffusion S.E. Solvent Evaporation SCO Spin Cross-Over SCXRD Single Crystal X-Ray Diffraction SEM Scanning Electron Microscopy terpy 2,2′:6′,2′′-terpyridine terpyO Deprotonated 2,6-bis(2-pyridyl)-4(1H)-pyridone terpyOH 2,6-bis(2-pyridyl)-4(1H)-pyridone terpyR 2,2′:6′,2′′-terpyridine substituted in the 4′-carbon position VF Vertex-to-Face xsolid Molar fraction in solid xsolid single co-crystal Molar fraction in single co-crystal xsolution Molar fraction in solution xˉ(xsolid) Sample mean of molar fraction in solid

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Statement of Original Authorship

The work contained in this thesis has not been previously submitted to meet requirements for an award at this or any other higher education institution. To the best of my knowledge and belief, the thesis contains no material previously published or written by another person except where due reference is made.

QUT Verified Signature Signature: __

Date: ______08-04-2014

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Acknowledgements

I would like to thank many people for their help and support during this long and turbulent journey.

To my principal supervisor and mentor Dr John McMurtrie: I thank you more than words can express for your help, guidance, support, wisdom and PATIENCE! Your perspective on things has made me a better chemist and a better critical thinker. Thank you for believing in me and for not giving up, you have made me realise that I could swim all along.

Thank you to my co-supervisor Dr Madeleine Schultz for all of the wisdom, advice, support, guidance and enthusiasm she has given me over the years. I thank you for your strength and encouragement, it has truly inspired me.

Thank you to A/Prof Dennis Arnold for his ideas, wisdom and unwavering support and for always telling me to keep going!

Thank you to Dr Llew Rintoul. I owe the success of all of the Raman spectroscopy studies to his help, advice and nuggets of insight.

Thank you to Dr Thor Bostrom, Dr Peter Hines and Lambert Bekessy for all of their help with SEM-EDX and to Tony Raftery for all of his help with PXRD and support. I could not have completed this research without it.

Thank you to AA/Prof John Bartley for helping me with ESI-MS and for teaching me how to navigate through the grey areas of NMR. I look at things differently because of that day.

I would like to thank Dr Edeline Wentrup-Byrne for encouraging me to pursue a career in chemistry, Dr Dalius Sagatys for sharing his infectious love of inorganic chemistry and Dr Jack Clegg for his encouraging words and suggesting I investigate oxalato complexes. I am on this path because of you.

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Supramolecular Selection in Molecular and Framework Co-crystals

Thank you to E/Prof Ray Frost and Dr Wayde Martens for introducing me to research and for the invaluable life-long skills they have taught me.

I would also like to thank Prof Godwin Ayoko, Prof Steven Bottle, Prof Peter Healy, A/Prof Peter Fredericks, A/Prof Eric Waclawik, AA/Prof Serge Kokot, Dr Tim Dargaville, Dr Kathryn Fairfull-Smith and Dr Kathleen Mullen for their support and kind words of encouragement when I needed them most.

Thank you to the technical staff for their insight and for training me to use the myriad of instruments I needed to complete this project. Thank you to Nick Ryan for listening and sorting things out. A big thank you to Elaine Reyes and Dean Rollbusch of HDR support for their help and patience and to the APA and the office of the DVC for financial support. Thank you to the team at the QUT IT helpdesk for going above and beyond when computers decided to have a mind of their own.

Thank you to my fellow postgraduate students, many of whom have become cherished friends. Special thanks (in alphabetical order) to Dr Sam Clifford, Priyanka Dey, Nic Forster, Branko Koncarevic, Vanessa Lussini, Jason Morris, Dr Svetlana Stevanovic and Hannah Wilson for understanding me, for their valuable friendship and for always knowing how to cheer me up. An extra special thank you to Michael Pfrunder for his help with all things SCXRD, for his friendship and support; I have found an unlikely but true friend in you!

I would like to thank my family and friends, for their encouragement and support during this long endeavour. Each one of you has enriched my life.

Lastly, I would like to thank my parents for believing in me and constantly telling me that they are proud of me. Dad, I thank you for logic and for your love, support and for being there whenever I need you. Thank you for listening to my chemistry woes and for asking me if there is anything you can do to help- I needed the laughs! Mum, I thank you for your infinite amounts of love, support and patience. Thank you for always giving me half of the story and for making me figure out the rest. Without you, I would not be the person I am today nor achieved the things I have achieved.

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“If we knew what it was we were doing, it would not be called research, would it?”

Albert Einstein

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CHAPTER 1: Introduction

1.1 Supramolecular chemistry

Over the past thirty years, supramolecular chemistry has evolved into a major field, which has stimulated countless multidisciplinary advances in domains within chemistry, biology and physics.1-3 The philosophical groundwork for supramolecular chemistry, specifically molecular recognition and host-guest chemistry was laid by Nobel laureate Hermann Emil Fischer in the late nineteenth century. Fischer was the first to postulate the lock and key analogy to describe enzyme-substrate interactions. In this model only a key (substrate) of the correct size and shape would fit into the lock (enzyme).4 However it was not until Pederson’s synthesis of crown ethers in 1960 and their subsequent application as ion-selective receptors by Lehn and Cram in 1987 that the concepts of supramolecular chemistry were beginning to be understood.5-13 Lehn, Cram and Pedersen won the Nobel Prize in 1987 for their work with cryptands and crown ethers that were capable of recognition and selectivity for metal ions.5,8-11 This work was a fundamental contribution into the research of molecular architectures, host-guest assemblies and molecular recognition.

This domain of chemistry was dubbed by Lehn as supramolecular chemistry and is defined by Lehn as “chemistry beyond the molecule” and the “chemistry of molecular assembly and of the intermolecular bond.”14-16 Unlike traditional strands of chemistry, such as organic chemistry, which concentrate on covalent bonding within molecules, supramolecular chemistry focuses on non-covalent interactions between molecules. Such interactions include hydrogen bonding, van der Waals forces, metal coordination and π-interactions, all of which are weaker and described as dynamic i.e. more easily reversed than covalent bonds.1-3

As Lehn’s definitions suggest, supramolecular chemistry focuses on the assembly of larger secondary structures through the arrangement of smaller molecular units via these non-covalent interactions. Lehn expands on these definitions by describing three overlapping phases that might be considered in the pursuit and design of highly

1

CHAPTER 1 complex materials where the ultimate goal is to design self-fabricating systems; molecular recognition, self-assembly and self-organisation through selection.1-3 Understanding the paradigms governing intermolecular interactions and subsequently manipulating those interactions is essential for the construction of functionally specific supramolecular systems.

1.2 Crystal engineering

The exploitation of supramolecular interactions to produce supramolecular crystalline solids with desired functionalities is the essence of crystal engineering.17-21 Crystal engineering is essentially a form of solid-state supramolecular synthesis.22

Schmidt in 1971 is usually credited for having conceived the expression crystal engineering in a publication reporting the light-induced photodimerisation of cinnamic acids in the solid state, however there is an earlier publication by Pepinsky in 1955 where the term crystal engineering is used for the very first time.23,24 Pepinsky demonstrated that by co-crystallising various organic ions with complex ions, one could control the packing in the resulting crystalline solid.24,25

Early research into crystal engineering focused on the exploitation of hydrogen bonds.26,27 More recently however, crystal engineering research has also involved exploitation of other intermolecular interactions such as metal-ligand coordination bonds and π-interactions. 28-35 Desiraju in Crystal engineering: The design of organic solids, 1989 defined crystal engineering as:

“the understanding of intermolecular interactions in the context of crystal packing and in the utilisation of such understanding in the design of new solids with desired physical and chemical properties”.36

To date, this is still the most widely accepted and quoted definition of crystal engineering.37,38 More recently Braga et al. in 2008 refined the definition of crystal engineering with a statement that captures the foundation of the research presented throughout this thesis:

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CHAPTER 1

“Making crystals by design is the paradigm of crystal engineering, the main goal being that of obtaining collective properties from the convolution of the physical and chemical properties of the individual building-blocks with crystal periodicity and symmetry”.39

These definitions of crystal engineering essentially involve the assembly of molecular fragments using intermolecular interactions to form crystalline materials. These molecular fragments are a substructural unit representative of the entire crystal structure and have been coined by Desiraju as supramolecular tectons, which are a direct analogy to the molecular tectons proposed by Corey for organic retrosynthesis.40 Supramolecular tectons are defined by Desiraju as:

“structural units within supramolecules which can be formed and/or assembled by known or conceivable synthetic operations involving intermolecular interactions”.27,41

Desiraju expanded on this definition by stating that supramolecular tectons are “kinetically defined structural units that express the core features of a crystal structure and which encapsulate the essence of crystals in terms of molecular recognition.”37

An understanding of molecular recognition interactions is a crucial part of crystal engineering due to the increasing ability to control the ways in which molecules associate during assembly.1,11,42 The ultimate goal of crystal engineering is to systematically design crystalline materials with specific functionalities by organising supramolecular tectons into predictable arrays.43,44 The chemical and physical properties of crystalline solids are influenced not only by the properties of the molecular components but also by their geometric arrangement and spatial distribution. However, it is important to note that crystal engineering is not synonymous with crystal structure prediction and although physical and chemical properties of the tectons can be controlled, it remains a challenge to definitively control or predict crystal packing.45-48 The frustration with this facet of crystal

3

CHAPTER 1 engineering has been expressed so eloquently by Maddox in 1988 in an article concerned with the ab initio calculations of silica, where he stated:

“One of the continuing scandals in the physical sciences is that it remains in general impossible to predict the structure of even the simplest crystalline solids from a knowledge of their chemical compositions.”49

Several years later Whitesell et al. in 1994 echoed the same dilemma concerning the prediction of crystal structures with the statement:

“There is as yet no generally successful approach to predicting, let alone controlling, molecular orientations in crystals. Thus the rational design and preparation of crystalline and other supra-molecular materials is hampered by insufficient knowledge of those factors that control packing.”50

Both sentiments still hold true today as ab initio crystal structure prediction is yet to come into fruition.48 This lack of modularity during the moleculecrystal process still remains a serious issue.37 At present we are still far off from being able to fully understand, predict or model the various forces responsible for the cohesion of solids from the knowledge of their molecular components.43

A quick glance at some of the structures deposited in the Cambridge Structural Database (CSD),51 which is a fully licensed and searchable database, illustrates that almost identical molecules can adopt very different crystal structures when crystallised using the same method. Similarly, various crystal structures are also reported for the same compounds crystallised from different solvent mixtures regardless of whether the solvent is detected in the eventuating solid. Currently the CSD contains almost 700 000 structures, which is more than double the number of structures that was available ten years ago; the number of structures in the CSD is observed to be exponentially growing. The increase in the volume of structures is largely due to the efficiency of data collection and refinement afforded by new advances in instrumentation, computation and structure visualisation. For many supramolecular chemistry research groups, crystal structure determination has become part of routine characterisation.

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The CSD is a vital research tool in realising the goal of crystal engineering and crystal structure prediction. Due to the enormous volume of structures available today it is possible to search for and identify similar molecules or tectons that lead to similar crystal packing arrangements or recurring supramolecular motifs, thereby identifying some element of modularity during the moleculecrystal process.43,47,52 Structures assembled using this building-block technique often display characteristic patterns, which are determined by intermolecular interactions between molecular units. Concerted sets of intermolecular interactions, which lead to supramolecular motifs or packing arrangements, often occur in the supramolecular structures of related compounds.53 These recurring motifs can be used as a basis for understanding the underlying supramolecular chemistry responsible for the overall spatial arrangement of molecular units.

The relevance of crystal packing to supramolecular chemistry has been articulated by Dunitz, who stated, “a crystal is in a sense, the supramolecule par excellence.”54 Thus, supramolecular interactions, which form a supramolecular motif, are by definition, infinitely repeated throughout the crystal with the utmost perfection. This perfection arises from the assembly that contributes the most stabilising lattice energy. If there is a correlation between the types of molecules and the packing arrangement they adopt, it is assumed that the crystal packing for those types of molecules is kinetically favoured and hence provides some basis from which to engineer similar compounds that may adopt the same motif or crystal packing.37,41

The use and exploitation of known crystal packing arrangements and recurring supramolecular motifs is the strategy that has been adopted during this research for the synthesis of new co-crystalline materials with predictable structures.

1.3 Intermolecular interactions

The term non-covalent interaction includes a wide range of forces involving fundamental attractive and repulsive interactions. Most of these forces, although generally considered weaker than conventional covalent bonds, are relied upon for

5

CHAPTER 1 the assembly of supramolecular architectures. Some of the fundamental non-covalent interactions in the realm of supramolecular chemistry, such as ionic, dipole, π-interactions and van der Waals forces will be discussed briefly in this section.

Bonds between charged species are formed through ion-ion interactions. These interactions are electrostatic in nature and therefore the associated energies can be calculated using Coulomb’s law. Coulombic forces are distance dependent to the approximate order of r-1 (where r is the distance separating the two charged species) and as such are considered as long range interactions.55 Ionic bonds are the strongest of intermolecular interactions with bond energies comparable in strength to covalent bonds ca. 100-350 kJmol-1.56,57 Figure 1 shows the structure of the highly symmetrical cubic crystal system of NaCl and illustrates that every Na+ cation (purple) is surrounded by six Cl- ions (green).58 Although strictly speaking NaCl is not considered a supramolecular entity, this simple example does illustrate that ions can arrange themselves into ordered structures using non-covalent ionic forces.

Figure 1: Sodium chloride cubic lattice system. Purple spheres represent Na+ ions, green spheres represent Cl- ions.

When NaCl is dissolved in water, the cubic lattice is disrupted by water solvation resulting in the formation of the highly labile octahedral hydrated Na+ complex, which is shown in Figure 2. In this example Na+ ions are bound to neutral but polar water molecules through ion-dipole interactions.

+ Figure 2: Octahedral labile [Na(H2O)6] complex.

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These ion-dipole interactions occur when lone pairs, such as those on oxygen atoms, are attracted to a cation with a formal positive charge. Coordinate bonds (dative bonds), which are mostly electrostatic in nature, fall under the umbrella of ion-dipole interactions. These types of interactions are observed in the solution and solid states and have bond energies of 50-200 kJmol-1.57 Although not strictly classed as intermolecular interactions, metals bound to poly-pyridyl ligands are examples of dative interactions (Figure 3).

z+ Figure 3: [M(bipy)3] complex (bipy = 2,2′-bipyridine) showing coordinate bonds between the metal cation and the nitrogen atoms of the ligands.

II 2+ Poly-pyridyl complexes of first row transition metals, such as [M (bipy)3] (MII = Fe, Ni, Co, Cu; bipy = 2,2′-bipyridine) are generally kinetically labile i.e. the ligands are not permanently bound to the metal. Polypyridyl complexes of Ru2+ such 2+ as [Ru(bipy)3] are kinetically inert and do not undergo ligand exchange under moderate conditions.59,60 Due to their kinetic inertness, poly-pyridyl complexes of Ru2+ have been extensively used as molecular units in supramolecular assemblies, co-crystallisation experiments and throughout this research project.35,57,61-66

For dipolar but non-ionic systems, dipole-dipole interactions involve the alignment of the partial positive charge of one molecule with the partial negative charge of another. The classic and possibly most widely used class of dipole-dipole interaction for supramolecular assemblies to control crystal packing is hydrogen bonding.26,27,38,57,67-83

Hydrogen bonding is electrostatic in nature and therefore distance dependant to the approximate order of r-1.84,85 A typical hydrogen bond has the form δ-D-H δ+···A δ-

7

CHAPTER 1 where D is the hydrogen bond donor, H is the hydrogen atom and A is the hydrogen bond acceptor. Systems that exhibit hydrogen bonding are those with hydrogen atoms that are bound strongly to electronegative donor atoms, such as oxygen, nitrogen and fluorine. It is generally accepted that there is a direct relationship between the strength of the hydrogen bond and the crystallographically determined distance between the bond donor and acceptor.57 Generally, the more electronegative the donor atom the larger the dipole moment, which in turn leads to stronger and often shorter hydrogen bonds. Stronger still are hydrogen bonds that occur when either D or A is charged with bond energies of up to 160 kJmol-1, a value comparable to weak covalent O-O peroxo bonds.57,67,72 Table 1 lists the calculated hydrogen bond dissociation energy for selected hydrogen bonding interactions in the gas phase.67

Table 1: Calculated hydrogen bond dissociation energy for selected hydrogen bonding interactions in the gas phase. H-bond Interaction* Energy (kJmol-1) H-bond Interaction* Energy (kJmol-1) [F-H-F]- 163 HOH···Bz 12 + [H2O-H-OH2] 138 F3-C-H···OH2 10 + [H3N-H-NH3] 101 NH3···Bz 9 - [HO-H-OH] 96 CH4···Bz 6 + NH4 ···OH2 80 HSH···SH2 4.5 + NH4 ···Bz 71 H2C=CH2···OH2 4 - HOH···Cl 56 CH4···OH2 1.3-3.3

O=C-OH···O=C-OH 31 C=CH2···C=C 2

HOH···OH2 19-21 CH4···F-CH3 0.84 *Values taken from The Hydrogen Bond in the Solid State by Steiner, 200267and references therein

Hydrogen bonds also display directionality along the D-H···A interaction with stronger hydrogen bonds exhibiting strong directionality tending to a D-H···A angle of 180° and weaker interactions exhibiting very weak directionality approaching angles of 90°. Jeffery in Introduction to Hydrogen Bonding, 1997 classified the various hydrogen bond interactions into three classes. Energetic and geometric properties of strong, moderate and weak hydrogen bond interactions are provided in Table 2.84

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Table 2: Energetic and geometric properties of strong, moderate and weak hydrogen bond interactions according to Jeffery, 1997.84 Strong Moderate Weak A-H···D interaction Mainly covalent Electrostatic Mainly electrostatic Bond energy (kJmol-1) 60-160 16-60 <16 Bond lengths (Å) H···D 1.2-1.5 1.5-202 2.2-3.2 A···D 2.2-2.5 2.5-3.2 3.2-4.0 Bond angles (°) 175-180 130-180 90-150 Directionality strong moderate Weak Gas phase dimers with Organic acids, C-H hydrogen bonds strong acids and bases alcohols and and O-H···π hydrogen Examples or interactions biological molecules bonds involving HF such as proteins Values adapted from Introduction to Hydrogen Bonding by Jeffery, 1997.57,84

The directionality of hydrogen bonds has been readily exploited for supramolecular crystal engineering such as in structures containing organic acids and bases.73,86-88 Hydrogen bonding is also heavily utilised by Nature as a determinant of the shape of many biological supramolecules, such as the overall geometry of proteins, recognition of substrates by enzymes and for the interactions between the base pairs in the two polynucleotide strands to form the double helix structure of DNA.57,68,85,89,90

π-Interactions are weak interactions that occur between systems with delocalised π-electrons such as those involving aromatic rings. Although relatively weak, these interactions have been exploited with great success specifically in the context of engineering supramolecules via self-assembly and for the control of crystal packing.28,91-93 In the context of this thesis, poly-pyridyl complexes such as II 2+ II [M (terpy)2] (M = Fe, Ni, Co, Cu, Ru) which are known to engage in π-interactions have been extensively used as molecular units in supramolecular assemblies and are therefore of particular interest.32-34,94-96

The exact nature of π-interactions is debated in the literature despite having been extensively studied in both naturally occurring and synthetic supramolecular systems.97-108 The atomic charge or electrostatic model is a widely accepted model for the explanation of the attractive forces between the aromatic groups partaking in

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π interactions.57,101-103,109 The hydrogen atoms in an aromatic system are electron-deficient and therefore carry a partial positive charge. The carbon atoms in these systems are electron-rich and therefore possess a partial negative charge.109 There are two main types of π-interactions; π-π interactions, sometimes referred to as π-stacking and CH···π interactions.109 For each type there are two main geometries, however due to the non-uniform charge distribution of aromatic systems, some interactions are energetically favoured over others.95,110,111

Face-to-face (FF) and offset-face-to-face (OFF) geometries are types of π-π interactions, which involve the faces of aromatic systems. The FF interaction, also known as the sandwich, is a direct overlap of the partially negatively charged carbon atoms (or of the partially positively charged hydrogen atoms) of two π systems. Due to the electrostatic repulsion of opposing like charges experienced by the system and hence the contribution of destabilising energy, this arrangement is rarely encountered.111 The OFF interaction, also referred to as parallel displaced or slipped face-to-face arrangement, contributes stabilising energy to a system, thus is encountered more frequently.102,103 In the OFF the partially positively charged hydrogen atoms of one aromatic system overlap the partially negatively charged carbon atoms of the other.97,99-101,104,112 These types of π-π interactions are responsible for the stacking arrangement of graphene sheets in graphite, hence graphite has applications as a lubricant due to the ability for the graphene layers to slip over each other.113 Similar stacking arrangements are observed between the aromatic groups of nucleobase pairs. These interactions are responsible for the stabilisation of the DNA double helix.89,90 Figure 4 illustrates the FF and OFF π-interactions using the benzene dimer as a model.

(a) (b)

Figure 4: Geometric arrangement for FF (a) and OFF (b) interactions of the benzene dimer as indicated by the double-headed red arrows.

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Edge-to-face (EF) and vertex-to-face (VF) are common examples of CH···π interactions and may be considered as weak hydrogen bonds between the electron-rich π system of an aromatic ring interacting with a partially electron-deficient hydrogen atom of another, resulting in an orthogonal geometric arrangement. As the terms suggest, EF and VF interactions occur when the edge (two hydrogen atoms) or the vertex (one hydrogen atom) of one aromatic system interacts with the planar face of another.97,103,105-108 Both of these CH···π interactions are illustrated using the benzene dimer in Figure 5.

(a) (b)

Figure 5: Geometric arrangement for EF (a) and VF (b) interactions of the benzene dimer as indicated by the yellow arrows.

The weakest of the intermolecular interactions to be introduced are called van der Waals forces. These forces are non-directional and depend on the proximity of adjacent nuclei to polarisable electron clouds, resulting in only weak electrostatic interactions in the order of about 5 kJmol-1. Due to the non-directional nature, van der Waals forces are a restricted tool for use in selective supramolecular design but have been found effective for the inclusion of small organic molecules in host-guest frameworks.96,114 This force is generally thought of as the product of two components; London dispersion forces (stabilising), which result from the interactions between fluctuating multipoles of adjacent molecules and exchange-repulsion (destabilising). Both components are distance dependant; the stabilising attraction component weakens with distances of r-6 while the destabilising short range exchange-repulsion decreases with interatomic separations of r-12. Therefore, van der Waals forces are stabilising except at close intermolecular contact distances.114

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1.4 Supramolecular motifs

The term supramolecular motif was briefly introduced earlier, and was defined as a set of recurring intermolecular interactions. Research conducted by Dance et al. concerning several primary and secondary motifs arising from various π-π and CH···π interactions are pertinent to this research.92,95,96,100,115,116 Motifs that involve phenyl groups have been described as multiple phenyl embraces however the term multiple aryl embraces is commonly used to collectively include non-phenyl aromatic systems such as pyridyl groups.100,116 Figure 6 illustrates some primary phenyl-phenyl OFF and EF conformations in aryl embraces between cation pairs of + Ph4P species. The parallel 4-fold aryl embrace (P4AE) involves one OFF and two EF interactions. The orthogonal analogue (O4AE) and the 6-fold aryl embrace (6AE) consist of only EF interactions. Secondary motifs are simply the infinite propagation of primary motifs throughout the crystal lattice.115-122

Parallel 4-fold aryl Orthogonal 4-fold embrace (P4AE) aryl embrace (O4AE)

6-fold aryl embrace (6AE) + Figure 6: Primary multiple aryl embrace motifs for Ph4P cations. The parallel 4-fold aryl embrace (P4AE) involves one OFF and two EF interactions. The orthogonal analogue (O4AE) and the 6-fold aryl embrace (6AE) consist of only EF interactions.

Multiple aryl embraces have been identified in the structures of a wide range of compounds with aromatic components including many of the poly-pyridyl coordination complexes discussed throughout this thesis.96,115 Multiple aryl embraces z+ z+ z+ between pairs of [M(terpy)2] , pairs of [M(phen)3] and pairs of [M(bipy)3] complexes are shown in Figure 7 (a)-(c). Due to the orthogonal conformation of the z+ terpy ligands in [M(terpy)2] complexes, pairs of complexes engage in a P4AE

12

CHAPTER 1 consisting of one OFF (red arrow) and two EF (yellow arrows) interactions. The propagation of these interactions forms the terpy motif, in which the complexes are arranged to form 2D-terpy embrace grid-like layers.32,34 This motif is highly relevant in the context of this thesis and will be discussed in greater detail in Section 4.1. z+ z+ Although the molecular structures of [M(terpy)2] and [M(phen)3] complexes differ (S4 versus D3 symmetry), the phen motif consists of the same interactions as those found in the terpy embrace and described as a P4AE.92,100 Akin to the terpy z+ embrace, the pair-wise interactions between two [M(phen)3] complexes comprises one OFF (red arrow) and two EF (yellow arrows) interactions. Unlike the terpy and z+ phen motifs, the recurring crystalline supramolecular motif between [M(bipy)3] complexes consists only of EF interactions. Dance et al. defines the bipy motif as a 6AE between six aromatic systems.95,96,115

(a) (b)

n+ n+ Pairs of [M(terpy)2] Pairs of [M(phen)3] complexes complexes

(c)

(a)

n+ Pairs of [M(bipy)3] complexes z+ z+ Figure 7: Multiple aryl embraces between pairs of [M(terpy)2] complexes, (a) [M(phen)3] z+ complexes (b) and [M(bipy)3] complexes (c). OFF interactions are represented by red double-headed arrows while EF interactions are represented by yellow arrows. The three remaining EF interactions z+ between the pair of [M(bipy)3] complexes (c) are obscured by the image.

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1.5 Lattice dimensionality

Wells in 1984 conceived topological rules that determine the connectivity and consequently the structural dimensionality for various molecular assemblies.123 These rules apply to repeat units that connect via a variety of intermolecular interactions, however within the context of this research, the lattice dimensionality of a supramolecular architecture is defined as the extent to which its building-blocks (repeat units) interconnect through coordinate bonds.

Zero dimensional (0D) structures contain discrete molecular units, which are self-contained and do not infinitely extend via coordinate bonds throughout the z+ z+ z+ lattice. Examples of such units include [M(terpy)2] , [M(phen)3] and [M(bipy)3] metal complexes. It is important to note that although intermolecular interactions z+ between [M(terpy)2] complexes form extended grid-like supramolecular motifs, these structures are defined within the context of this thesis to be molecular and not polymeric structures as propagation is via π-π and CH···π intermolecular interactions and not coordinate bonds.

For structures of higher dimensionality, building-blocks must have at least two free connecting links available for bonding to its neighbours.17,124 One-dimensional structures (1D) are those where the molecular units are interconnected via two links to produce polymeric structures that are infinite in one direction through the crystal lattice. Examples of 1D structures include linear and zig-zag chains. A two-dimensional structure (2D) involves building-blocks that are interconnected by at least three points (coplanar). Examples of these include square grids and honeycomb structures. Three-dimensional frameworks (3D) arise when building-blocks are interconnected by at least three non-coplanar links. Some common 3D scaffolds include infinite matrices and diamondoid structures.17,124 Figure 8 shows schematic representations of example 1D (a), 2D (b) and 3D (c) topologies.

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(c)

3 connected points (non-coplanar)

(b)

3 connected 4 connected points points (coplanar) (non-coplanar)

(a)

4 connected 6 connected 2 connected points points points (coplanar) (non-coplanar) Figure 8: Schematic representations of (a) 1D linear chain, (b) grid (bottom) and honeycomb (top) 2D lattices and (c) matrix (bottom), diamondoid (middle) and extended (top) 3D networks. The building- blocks and their connectivity are also shown to the right of each structure to illustrate the relationship between building-block connectivity and the resulting dimensionality of the structure.17,124

The nomenclature of 1D, 2D and 3D metal-organic framework structures has recently been the topic of debate, specifically in regards to the synonymous use of the terms “coordination polymer”, “coordination frameworks/network” and “metal-organic framework/network”.125,126 Throughout this thesis, 3D structures are referred to using the terms coordination framework and metal-organic framework interchangeably.

1.6 Multicomponent crystals

1.6.1 Nomenclature

The nomenclature of crystal forms that contain more than one component is currently an active subject of debate, especially in regards to the distinction between polymorphs, solvates/hydrates, molecular salts and co-crystals.39,127-136 The discussion in the literature is especially heated in regards to the design and patenting of active pharmaceutical ingredients.137-144

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In a letter titled Crystal and Co-crystal, 2003 Desiraju expressed that “problems with nomenclature are necessary evils in the development of a new subject”.131 Research into multicomponent crystals is not a relatively new topic, but has recently become one of the most attractive and fast growing areas in crystal engineering.136 The term “co-crystal”, which has been used for some time,145 has specifically been a subject of disagreement. Desiraju expressed that “co-crystal” must apply to crystals together with other crystals, with each component retaining its individual crystalline identity and that previously used terms such as molecular complex are more acceptable to describe crystals with different components contained in the same lattice.131

Dunitz in 2003 stated that the term molecular complex was too broad and not necessarily connected to compounds in the crystalline state. Dunitz defined co-crystals as “crystals containing two or more components together” further stating that although the term has its flaws it has been firmly established in the literature.132 This definition has been expanded by Stahly who stated “co-crystals consist of two or more components that form a unique crystalline structure having unique properties”.134,135 However, both of these definitions are too broad as they “encompass molecular compounds, molecular complexes, solvates, inclusion compounds, channel compounds, clathrates, and possibly a few other types of multi-component crystals”.129,132 A more specific definition restricts the use of the term co-crystal to denote multicomponent crystals that are composed of molecular components that are solids in their pure form under ambient conditions, versus those that are composed of a solid together with a liquid, the latter of which are called solvates or pseudopolymorphs.81,127-129,133-136 This definition implies that molecular components abandon their individual crystalline identity within the co-crystal to form a single crystalline phase.129

A thorough survey of the literature reveals that co-crystals, specifically those containing transition metal coordination compounds, have been labelled under several different terms. In addition to the term “co-crystal”, other common terms that have been used include “solid solutions”,28,61,62,146-154 “metal dilution compounds” or “diluted systems”,155-169 “metallic doped systems/compounds”,170-182 “mixed crystals”,65,74,183-199 and “molecular/supramolecular alloys”.79,200-202 Many of these terms

16

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(more of which can be found in the keywords section of this thesis) are used interchangeably, and some terms such as “mixed crystal” have been used extensively to describe compounds such as simple salts and are therefore ambiguous.203-207

The inconsistency in the nomenclature of these compounds has caused unnecessary confusion and misunderstandings. Moreover, it has added difficulty in the search for compounds in the literature. To avoid confusion the term “co-crystal” is used throughout this thesis to describe crystals that contain multiple molecular components, specifically, two or more different types of metal complexes. The terms “diluted”, “undiluted” and “dilution” are used to aid in the discussion of co-crystals and co-crystallisation experiments involving systems that contain more than two types of metal complexes. For example, in pure compounds of AB where A is a cationic metal complex and B is an anionic metal complex, co-crystallisation experiments can be performed that dilute A to yield a system of AxA′1-xB or to dilute

B resulting in a ABxB′1-x system (A′ and B′ are complexes capable of substituting for A and B respectively). Herein, the former is called a cationic metal complex dilution while the latter is called an anionic metal complex dilution.

1.6.2 Co-crystal systems in the literature

As mentioned earlier, an ongoing challenge in the field of supramolecular chemistry and crystal engineering is the development of methods for reliably exploiting intermolecular interactions to form new materials with specific functionalities and predictable crystal structures. One approach to forming new materials with predictable structures that is gaining popularity is through the synthesis of co-crystals via the co-crystallisation of species that possess similar molecular and crystal structures but different physical or chemical properties. The resulting crystals often form with predictable structures and have properties that may be tuned by modulating the relative concentration of the components in the co-crystallising solution.

17

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Although co-crystals are relatively recent in the synthetic realm, co-crystals in Nature, specifically metallic doping of minerals, dates back for millennia.208 For example, corundum, a naturally occurring crystalline form of aluminium oxide

(Al2O3) is in its purest form colourless and transparent. However, by substituting a small fraction of the Al3+ cations in the otherwise unchanged structure with Cr3+ or Ti3+ cations, properties such as colour change to red and blue to yield ruby and sapphire respectively.25,209-211

A substantial number of co-crystals that are reported in the literature are those of organic salts that form via hydrogen bonds between acidic organic compounds e.g. carboxylic acids and phenols with amines.81,88,127,212-221 This section will discuss co-crystal systems of metal-organic compounds formed via the co-crystallisation of two or more coordination complexes, that differ from one another in the metal centre or in the metal centre and ligands with specific focus on the methods used to ascertain the ratios of each complex present in the solid.

Throughout the literature, the term “metal dilution” has been used to describe the process by which a metal ion, usually Cr2+/3+ or Fe2+/3+ is substituted by Zn2+ or Al3+ to modulate the properties of a metal complex such as spin cross-over (SCO). The greater the proportion of the inactive Zn2+ or Al3+ relative to Cr2+/3+ or Fe2+/3+, the more highly diluted the compound. Research in this area by Gütlich et al., which began over three decades ago, investigated metal dilution effects on the spin cross- over (SCO) property of highly diluted compounds such as

II II 147-149,183,222-226 [FexM 1-x(2-pic)3]Cl2·2EtOH (M = Co, Zn; 2-pic = 2-picolylamine),

227,228 II [FexZn1-x(ptz)6](BF4)2 (ptz = 1-propyltetrazole), [FexM 1-x(phen)2(NCS)2] II II (M = Mn, Co, Ni, Zn; phen = 1,10-phenanthroline) and [FexM 1-x(L)3](ClO4)2 (MII = Mn, Ni, Zn; L = 1,10-phenanthroline, 2,2′-bipyridine).149-151,156,170 Overall results suggested that the cooperativity of the SCO was reduced with increased metal dilution. Furthermore, the effect of metal dilution on the SCO temperature was found to be loosely predictive based on the ionic radius of the dilutant ion; larger ions such as Zn2+ were found to lower the SCO temperature and stabilise the high-spin form of the material.

18

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188- More recent investigations into the electronic properties of [FexZn1-x(ptz)6](BF4)2,

191,229-233 160,161,234,235 [FexZn1-x(phen)2(NCS)2], and related compounds such as

II II 152,196,197,236-238 [M 1-xFex(btr)3](ClO4)2 (M = Co, Ni; btr = 4,4′-bis-1,2,4-triazole),

166,198 [Zn1-xFex(bbtr)3](ClO4)2 (bbtr = 1,4-di(1,2,3-triazol-1-yl)-butane) and

[FexZn1-x(bapbpy)(NCS)2] (bapbpy = N6,N6′-di(pyridin-2-yl)-2,2′-bipyridine-6,6′- diamine)168 reached similar conclusions as those from earlier work. It is interesting especially in relation to this thesis that all work and measurements were made on the bulk crystalline or powdered material, while none reported measurements on deliberately mixed samples (not co-crystallised), which could have been used as a control. Furthermore, no mention was made regarding the composition of individual co-crystals or the homogeneity or lack thereof of the bulk sample. The compositions of the materials in all of these studies were based on measurements taken from bulk polycrystalline or powdered material using techniques such as elemental microanalysis (C, H, N), X-ray fluorescence (XRF), powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS).

A B A Over the last five years co-crystallisation systems of [M xM 1-x(bpp)2]X2 (M and MB are combinations of Mn2+, Fe2+, Co2+ and Zn2+; bpp = 2,6-bis(pyrazol-3- - - - yl)pyridine (shown in Figure 9); X = NCS , NCSe , BF4 ) have been subjected to numerous spin-state studies.153,162,164,193-195 Although some report single crystal SCO measurements,162 the proportions of each metal complex in all of the reported diluted systems were either elucidated using bulk measurement techniques such as lattice dimension changes via PXRD or assumed to be the same as the ratio of the complexes in the starting solution. In a related study concerning the system

[FexCo1-x(bpa)2](NCS)2 (bpa = 1,3-bis(4-pyridyl)propane), the authors note that the metal-nitrogen bond lengths as measured via single crystal X-ray diffraction (SCXRD) were approaching the lengths usually observed for the pure cobalt compound, yet conclude that the diluted system has the same ratio of metal complexes to that which was present in solution (x = 0.50).194

19

CHAPTER 1

Figure 9: 2,6-bis(pyrazol-3-yl)pyridine (bpp)

II 2+ Co-crystallisation systems that involve [M (terpy)2] and related complexes, especially systems where different metal complexes are co-crystallised together are of particular interest. Halcrow et al. were the first to report SCO co-crystallisation systems that incorporated two different metal complexes to give the formula II II II [M (1-bpp)2]x[M (terpy)2]1-x(BF4)2 (M = Fe, Co, Ru; 1-bpp = 2,6-bis(pyrazol-1- yl)pyridine; terpy = 2,2′;6′,2′′-terpyridine) by exploiting the similarities between the lattices of the pure structures that arise from similar π-intermolecular interactions.61,62,153 Figure 10 shows the structures of the ligands used.

Figure 10: (left to right) 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) and 2,2′;6′,2′′-terpyridine (terpy)

PXRD of the bulk polycrystalline material was used to ascertain information relating to structure and crystallinity of these systems. The PXRD patterns of the

[Fe(1-bpp)2]x[Ru(terpy)2]1-x(BF4)2 system are reported to broaden significantly as the ratio of complexes approaches 0.50. Furthermore, the authors note that as the fraction of the ruthenium complex increases (as determined by microanalysis (C, H, N) on polycrystalline material), the larger the diffraction peak associated with the pure ruthenium complex, thus giving rise to samples that contain two phases. The authors conclude that a single phase is present only in systems with a high proportions of the

II 2+ 61,153 [M (1-bpp)2] complex.

Also pertinent to the research presented within this thesis are co-crystallisation III 3- systems containing [M (ox)3] complexes (ox = oxalate), especially in regards to the methods used to quantify the ratio of metal complexes present in the crystalline III III state. Metal dilution systems such as Mg[NaAlxM 1-x(ox)3] (M = Ti, V, Cr, Mn, Fe,

175-181,239-244 A B III A B 2+ Co), NBu4[M xM 1-xM (ox)3] (M and M are combinations of Cr ,

2+ 2+ 2+ 2+ 2+ III 184,245-247 II A B II Mn , Fe , Co , Ni and Zn ; M = Cr, Fe), NBu4[M M xM 1-x(ox)3] (M

20

CHAPTER 1

= Cr, Mn, Fe; MA and MB are combinations of Al3+, Cr3+, Mn3+ and Fe3+),185-187,248-250 A B III A B 2+ 2+ 2+ and [M xM 1-x(L)3][NaM (ox)3] (M and M are combinations of Co , Zn , Ru 2+ III II A B II and Os ; M = Al, Cr, Rh) and [M (L)3][NaM xM 1-x(ox)3] (M = Co, Zn, Ru, Os; MA and MB are combinations of Al3+, Cr3+ and Rh3+)64,65,182,192,251-253 have been extensively studied for their photophysical and electronic properties as well as for their magnetic susceptibility.

III 3- In an overwhelming majority of these studies involving [M (ox)3] , the measurements including those for determining the ratio of metals in the solid are reported only for the bulk polycrystalline or powdered material. Of those that report the investigated phenomena for single crystals, the characterisation method used to quantify the metal ratio (x) in the solid was either unclear or not mentioned,182,242,244 calculated from bulk measurements such as PXRD and ICP-MS,65 calculated for single crystals but unclear if only one co-crystal or multiple co-crystals grown from each solution was analysed,243,253 or assumed to be the same as that which was present in the crystallising solution.239 Furthermore, no mention with regards to the homogeneity of the bulk crystalline material is made. In a few cases the authors note that the effective solid-state concentration was different from the initial concentration present in solution, however no suggestions are given as to why this might be.64,65,182,192,252-254

Specifically with regards to the research presented within this thesis, an important milestone in the field of co-crystals was published in 2000 by MacDonald et al.74 In II this work, isomorphous salts of the formula (imidazolium)2[M (dipic)2]·2H2O (dipic = pyridine-2,6-dicarboxylate) metal complexes were co-crystallised in varying ratios A B A B to give single co-crystals of (imidazolium)2[M xM 1-x(dipic)2]·2H2O (M and M are combinations of Mn2+, Co2+, Ni2+, Cu2+, and Zn2+). Analysis of these single co- crystals was by AAS, inductively coupled plasma-mass spectrometry (ICP-MS), and neutron diffraction. Results of these analyses indicated that the concentration of the different metal complexes (associated with MA and MB) in the single co-crystals was directly dependant on the ratio of the complexes in the co-crystallising solution. For example, co-crystals formed from a 0.50:0.50 mixture of A B (imidazolium)2[M (dipic)2]·2H2O and (imidazolium)2[M (dipic)2]·2H2O were

21

CHAPTER 1

A B found to have the formula (imidazolium)2[M 0.50M 0.50(dipic)2]·2H2O, whereas co-crystals formed from solutions containing 0.80:0.20 of the same two complexes A B were found to have the formula (imidazolium)2[M 0.80M 0.20(dipic)2]·2H2O. Photographs of representative co-crystals grown from various co-crystallising solutions are shown in Figure 11.

20% Cu 40% Cu 60% Cu 40% Ni 33% Ni 80% Co 60% Zn 40% Mn 60% Co 33% Co 33% Cu A B Figure 11: Photographs of (imidazolium)2[M xM 1-x(dipic)2]·2H2O co-crystals with the metals and their respective ratios given under each image.74

Ordinary XRD as a means of determining the order/disorder of the metals in the crystal lattice was bypassed since it detects electron density and therefore cannot easily distinguish between atoms such as nickel and cobalt. Neutron diffraction was instead used and the authors concluded that it was most likely that the metals were randomly disordered within the crystal lattice. Furthermore, these results indicated that the rates of crystallisation of all the metal complexes involved were comparable, as the concentrations in the crystalline state matched the solution concentrations.74 In these co-crystals, the complexes interact via charge-assisted hydrogen bonds between the carboxylic acid groups of the dipic ligands and the imidazolium cations. The report published by the authors is a rare example in the literature in which synthetically engineered single co-crystals have been specifically analysed to directly determine the relative concentrations of the different molecular components and the distribution of the metals in the crystal structure.

Taking advantage of the close structural match between the various types of pure II (imidazolium)2[M (dipic)2]·2H2O compounds, the authors also report the formation of epitaxial growth crystals where seed crystals of one type of metal complex were immersed into solutions containing a different complex.74,255 Interestingly, the authors

22

CHAPTER 1 report that due to the directionality of the hydrogen bonds within the lattice, epitaxial growth was more favoured in the direction that propagates via hydrogen bonding giving rise to faster growth on the [100] face over the [001] face. Growth onto the [001] face was found to be promoted by seeding a co-crystal into the crystallising solution.255

Since the milestone reported by MacDonald et al., a handful of studies into single co-crystals and epitaxial growth crystals exploiting hydrogen bonding between complexes have been published.28,79,80,201,256-260 A significant contribution to the field of single co-crystal analysis that is especially relevant to the work presented in this thesis has been reported by Hosseini and co-workers.

Hosseini et al. reported the synthesis of numerous co-crystals based on isomorphous structures containing the cationic techton, [1,4-bis(amidinium)benzene]2+ co- z- 3+ 2+/3+ 3+ 2+ crystallised with two or more [M(CN)6] (M = Cr , Fe , Co , Ru ) complexes. The single crystals, which were grown from aqueous mixtures containing the respective species, were characterised by SCXRD, infrared spectroscopy and scanning electron microscopy equipped with energy dispersive X-ray analysis (SEM- EDX) and were found to be isomorphous with the pure compounds and to contain only the desired molar ratio of the respective metal complexes.80,201 The reliability by which these crystals form allowed the authors to conduct in-depth studies into multi-step epitaxial growth using the same molecules as building-blocks. The first epitaxial growth crystal denoted by the authors as “Generation 1” (G-1), were grown in a similar manner to that of the co-crystals described previously with II 4- slight modifications. Instead of incorporating multiple [M (CN)6] complexes into II 4- the one solution, a seed crystal containing only one type of [M (CN)6] complex II 4- was grown first and then immersed into a solution containing another [M (CN)6] complex (MII = Fe, Ru). The result was the formation of crystals with two visibly defined domains, a core domain encapsulated by a “shroud” domain. Crystals were sliced to expose both domains and each domain was shown by SEM-EDX to contain II 4- only one [M (CN)6] complex. Newer generation epitaxial crystals with three (G-2) and four (G-3) domains, with each domain either containing one or two different

II 4- 80 [M (CN)6] were successfully synthesised using a multi-step approach. Figure 12

23

CHAPTER 1 shows images of sliced epitaxial growth crystals from G-1, G-2 and G-3 experiments, which clearly show the various domains.

Figure 12: Photographs of slices of G-1 (a, b), G-2 (c, d) and G-3 (e, f) epitaxial growth crystals clearly showing the different Ru-containing domains (colourless) and Fe-containing domains (yellow/orange).80

Subsequent research into these epitaxial materials focused on determining the concentration of the various metal complexes at the interface between the domains. Transmission electron microscopy (TEM) and scanning transition electron microscopy (STEM) coupled with EDX analysis were employed to characterise the visually defined crystalline boundary.256,257 Results indicated the presence of a diffuse interface, as EDX detected all metals involved on either side of the visual boundary. In the case of the G-1 Ru (core)/Fe (shroud) system, mapping analyses using these techniques revealed the interface to contain an area containing approximately 50% of each metal complex. The authors attribute the diffusion at the interface to partial surface dissolution of the seed crystal during epitaxial growth.256,257

One very recent study by Dehghanpour and co-workers in 2013 utilised characterisation techniques such as SCXRD, AAS and ICP-MS to analyse single A B A B 2+ 2+ co-crystals of [M xM 1-xL2(NO3)2]n, (M and M are combinations of Co , Zn and Cd2+; L = 3-(2′-pyridylmethyleneamino)pyridine). Akin to the ground-breaking research by MacDonald and Hosseini, the relative ratios of metal complexes in these co-crystals were also found to be directly related to the relative concentration of the complexes in solution.260

24

CHAPTER 1

The assumptions regarding the uniformity and homogeneity of co-crystals grown from solutions containing mixtures of metal complexes that have been reported by others seems to be supported by the results of MacDonald, Hosseini and Dehghanpour. It was therefore interesting to observe if co-crystallisation systems of other common metal complexes that are known to form isomorphous structures also yield similar results.

1.6.3 The discovery of supramolecular selection

Recently published research that was conducted by the candidate during the candidate’s Honours project reported the exploitation of supramolecular motifs to form single co-crystals of a predictable structure containing two or more different metal complexes.35,261 The initial aim of this work was to assess the potential for the formation of molecular co-crystals where the interactions between building-blocks were built upon π-interactions. The following discussion summarises the research published by Bouzaid et al.35

Two systems of binary molecular single co-crystals were prepared and analysed for A B A B A composition and phase: [M xM 1-x(phen)3](PF6)2 and [M xM 1-x(bipy)3](PF6)2 (M and MB are combinations of Fe2+, Ni2+ and Ru2+.35,261 Specific focus was placed on elucidating the homogeneity of co-crystals grown from the same solution and the relationship between the ratio of metal complexes in the solution to that present in the crystalline state.

A B A B Molecular co-crystals of [M xM 1-x(phen)3](PF6)2 and [M xM 1-x(bipy)3](PF6)2 were A prepared by co-crystallisation from evaporating solutions of [M (L)3](PF6)2 and B [M (L)3](PF6)2 (L = phen or bipy) metal complexes in acetone and water. The relative molar ratios of the two complexes in solution (xsolution) ranged from 0.90:0.10 to 0.10:0.90 in 0.10 increments giving a total of nine co-crystallisation experiments per series. Three series of co-crystallisation experiments were prepared for each type of molecular co-crystal where the combinations of MA and MB were Fe2+/Ni2+, Fe2+/Ru2+ and Ni2+/Ru2+. Each co-crystallisation experiment was performed in

25

CHAPTER 1 duplicate and in each case co-crystallisation was allowed to continue until no obvious colour remained in the mother liquor indicating that only negligible amount of the complexes remained in solution.

Crystallised samples were visually assessed under an optical microscope equipped with a polariser for evidence of co-crystallisation. Crystals of pure

[Ni(phen)3](PF6)20.5H2O and [Ni(bipy)3](PF6)2 are light pink while those of

[Ru(phen)3](PF6)20.5H2O and [Ru(bipy)3](PF6)2 are red. The appearances of the

[NixRu1-x(phen)3](PF6)20.5H2O and [NixRu1-x(bipy)3](PF6)2 co-crystals were found to be visually indistinguishable from those of the respective pure ruthenium complex.

Complexes of [Fe(phen)3](PF6)20.5H2O and [Fe(bipy)3](PF6)2 are also red, thus the same was observed for experiments that produced co-crystals of

[NixFe1-x(phen)3](PF6)20.5H2O and [NixFe1-x(bipy)3](PF6)2. The appearances of all of the co-crystals within a given batch with respect to habit and colour were very similar. In none of the experiments involving the nickel complex were pink crystals observed.

Microscopic images of single crystals of [Ni(phen)3](PF6)20.5H2O,

[Ru(phen)3](PF6)20.5H2O and representative single co-crystals of

[NixRu1-x(phen)3](PF6)20.5H2O obtained by co-crystallisation of an equimolar mixture of the two pure complexes are shown in Figure 13. Crystals of the pure

[Fe(L)3](PF6)2 and [Ru(L)3](PF6)2 (L = phen or bipy) complexes are visually very similar and therefore experiments involving both were not able to be qualitatively assessed using visual inspection.

26

CHAPTER 1

[Ni(phen)3](PF6)20.5H2O [Ru(phen)3](PF6)20.5H2O

1 mm 1 mm

[NixRu1-x(phen)3](PF6)20.5H2O

1 mm

Figure 13: Microscope images of single crystals of [Ni(phen)3](PF6)20.5H2O, [Ru(phen)3](PF6)20.5H2O and single co-crystals of [NixRu1-x(phen)3](PF6)20.5H2O obtained by co-crystallisation of an equimolar mixture of the two pure complexes. Crystals of pure

[Ni(phen)3](PF6)20.5H2O are light pink while those of [Ru(phen)3](PF6)20.5H2O are red. The appearances of the [NixRu1-x(phen)3](PF6)20.5H2O are visually indistinguishable from those of the pure ruthenium complex.35

Single co-crystals were also screened by high-resolution electrospray ionisation mass spectrometry (ESI-MS) to qualitatively confirm co-crystallisation of the metal complexes. The presence of peaks corresponding to ions that are specific for each metal complex in the mass spectra afforded quick and conclusive confirmation that both complexes were present in each individual single co-crystal. For example, Figure 14 shows an ESI mass spectrum collected from a single co-crystal grown from a solution containing an equimolar ratio of [Ni(phen)3](PF6)2 and

[Ru(phen)3](PF6)2.

27

CHAPTER 1

1 +ESI Scan (0.247-0.827 min, 37 scans) Frag=120.0V [Ni0.5Ru0.5(phen)3(PF6)2.d Subtract x10 299.0704 1 x10 + 743.1057 [Ru(phen)3](PF6)

8 4

3 + 6 [Ni(phen)3](PF6) 321.0556 787.0748 2 743.1057

4 1

787.0748 2 0 742 746 750 754 758 762 766 770 774 778 782 786 790 Counts (%) vs. Mass-to-Charge (m/z)

0 300 340 380 420 460 500 540 580 620 660 700 740 780 Counts (%) vs. Mass-to-Charge (m/z) Figure 14: Representative ESI mass spectrum obtained for a single co-crystal produced from a solution containing an equimolar mixture of [Ni(phen)3](PF6)2 and [Ru(phen)3](PF6)2. The spectrum has peaks indicative of the presence of ions associated with each metal complex thus confirming that both complexes were present in the single co-crystal.35

The spectrum in Figure 14 clearly shows the presence of peaks for m/z 299.0704 2+ + 2+ ([Ni(phen)3] ), m/z 743.1057 ([Ni(phen)3] + PF6] ), m/z 321.0556 ([Ru(phen)3] ) + and m/z 787.0748 ([Ru(phen)3] + PF6] ). ESI-MS was used to screen at least three crystals from each batch of co-crystallisation experiments, and in each case, the co-crystals were found to contain both metal complexes, thus confirming co-crystallisation.

Powder X-ray diffraction patterns of all the pure complexes as well as for the co-crystals harvested from solutions which contained complexes in ratios of 0.80:0.20, 0.50:0.50 and 0.20:0.80 were collected for both the A B A B [M xM 1-x(phen)3](PF6)20.5H2O and [M xM 1-x(bipy)3](PF6)2 systems. The PXRD patterns for both systems are shown in Figure 15.

28

CHAPTER 1

Powder XRD of [M(phen)3](PF6)2 system Powder XRD of [M(bipy)3](PF6)2 system

2 1

70000.00 1

-

-

-

102

10

420

20

51

1

-

11

2

-

311

002

-

2

602

11

1

-

-

13

100

62 200

2

004

800 112 [Fe(phen)3](PF6)2 42 [Fe(bipy)3](PF6)2 60600.00 60000.00 0.80Fe:0.20Ru 0.80Fe:0.20Ru

0.50Fe:0.50Ru 0.50Fe:0.50Ru 50600.00 50000.00 0.20Fe:0.80Ru 0.20Fe:0.80Ru

[Ru(phen)3](PF6)2 [Ru(bipy)3](PF6)2

40000.00 40600.00

0.20Ni:0.80Ru 0.20Ni:0.80Ru

0.50Ni:0.50Ru 0.50Ni:0.50Ru 30000.00 30600.00 0.80Ni:0.20Ru

0.80Ni:0.20Ru

Counts Counts [Ni(phen)3](PF6)2 [Ni(bipy)3](PF6)2 20000.00 20600.00 0.20Fe:0.80Ni 0.20Fe:0.80Ni

0.50Fe:0.50Ni 0.50Fe:0.50Ni 10000.00 10600.00 0.80Fe:0.20Ni 0.80Fe:0.20Ni

[Fe(phen)3](PF6)2 [Fe(bipy)3](PF6)2 0.00 600.00 88 99 1010 1111 1212 1313 1414 1515 1616 1717 1818 1919 2020 2121 2222 2323 2424 99 1010 1111 1212 1313 1414 1515 1616 1717 1818 1919 2020 2121 2222 2323 2424 Position ( 2θ) Position ( 2θ)

Figure 15: Powder XRD patterns of respective pure [Fe(L)3](PF6)2 (red), [Ru(L)3](PF6)2 (blue), and [Ni(L)3](PF6)2 (green) interspersed with the PXRD patterns for respective co-crystals obtained from solutions containing 80:20, 50:50, and 20:80 molar ratios of the metal complexes. The A B A B [M xM 1-x(phen)3](PF6)20.5H2O system is shown on the left, while the [M xM 1-x(bipy)3](PF6)2 system is shown on the right.35

The PXRD patterns of the co-crystals were found to match the patterns of the pure compounds. The experimental powder patterns were also found to match the patterns simulated from experimental SCXRD data collected from the pure nickel and ruthenium complexes as well as patterns simulated from SCXRD data collected from co-crystals grown from solutions that contained equimolar ratios of complexes. The similarities between the experimental powder patterns within each respective system and with those simulated from experimental SCXRD data indicated that the co- crystals were isomorphous with the pure samples and were of a single phase.

As the products of the co-crystallisation experiments were confirmed to be co-crystals, elemental analysis of single co-crystals was obtained using SEM-EDX to quantify the ratio of metal complexes present. At least three co-crystals from each batch were analysed to determine if any variation (with respect to the ratios of metal complexes) was present in co-crystals harvested from the same solution. In addition, each co-crystal analysed was measured in three different locations to test for any

29

CHAPTER 1 intracrystal concentration gradients. The results from the SEM-EDX analysis of co-crystals of [NixRu1-x(phen)3](PF6)20.5H2O are shown in the plot in Figure 16.

SEM-EDX of [NixRu1-x(phen)3](PF6)2 series 11.00.00 01.00.00

00.90.90 00.90.10

00.80.80 00.80.20

in solidin in solidin 00.70.70 00.70.30

00.60.60 00.60.40 complex

00.50.50 00.50.50 Ru

00.40.40 00.40.60

00.30.30 00.30.70

00.20.20 00.20.80 Mole fraction of Ni complexNifractionof Mole 00.10.10 00.10.90 fractionofMole

00.00.00 10.00.00 0.00 00.10.10 00.20.20 00.30.30 00.40.40 00.50.50 00.60.60 00.70.70 00.80.80 00.90.90 1.00

Mole fraction of Ni complex in solution

Figure 16: Scatter plot and regression line for SEM-EDX analyses of [NixRu1-x(phen)3](PF6)20.5H2O co-crystals. Note that the metal ratios in [NixRu1-x(phen)3](PF6)20.5H2O co-crystals from each batch are very similar.35

For the plot shown in Figure 16 the horizontal axis labelled “Mole fraction of Ni complex in solution” represents the different mole fractions of the nickel complex that were present in solution. The vertical axis, labelled “Mole fraction of Ni complex in solid”, refers to the x variable in the [NixRu1-x(phen)3](PF6)20.5H2O co-crystal formula. Since the ratios of the metal complexes were normalised to one, the fraction of the ruthenium complex present in the co-crystals were calculated by subtracting the fraction of the nickel complex (x) from one (1-x).

30

CHAPTER 1

EDX measurements from different areas on the same [NixRu1-x(phen)3](PF6)20.5H2O co-crystal gave almost identical ratios of metals. The data shown in Figure 16 for the

[NixRu1-x(phen)3](PF6)20.5H2O series also indicated that the ratios of metals in each co-crystal analysed from a single batch were also almost identical such that xsingle co-crystal 1 = xsingle co-crystal 2. For example the co-crystals obtained from a solution containing 10% [Ni(phen)3](PF6)2 were found to have a nickel mole fraction of 0.10 and hence the co-crystals from that batch have the formula

[Ni0.10Ru0.90(phen)3](PF6)20.5H2O. Similarly, analysis of co-crystals from the other batches within this series confirmed a direct relationship between the metal ratios of the complexes in the solid and their respective concentrations in solution such that xsolid = xsolution. The scatter plots generated from SEM-EDX data for all combinations A B of [M xM 1-x(phen)3](PF6)20.5H2O yielded similar results to the

[NixRu1-x(phen)3](PF6)20.5H2O plot shown in Figure 16. To provide final confirmation of these results, samples of [Co(phen)3](PF6)2 and [Cu(phen)3](PF6)2 were also prepared and these were simultaneously co-crystallised with

[Fe(phen)3](PF6)2, [Ni(phen)3](PF6)2 and [Ru(phen)3](PF6)2 in a 1:1:1:1:1 ratio. Ten co-crystals that were grown from this solution were analysed by SEM-EDX in the same manner as for binary co-crystals. An example of an EDX spectrum showing peaks associated with each of the five complexes can be found in Appendix A. Each of the ten co-crystals analysed was found to contain all five complexes in approximately a 1:1:1:1:1 ratio. Thus, results concerning A B [M xM 1-x(phen)3](PF6)20.5H2O systems were consistent with the assumptions reported by others regarding the uniformity and homogeneity of co-crystals grown from solutions containing mixtures of metal complexes.

II II The crystals of pure [M (phen)3](PF6)20.5H2O (M = Fe, Ni, Ru) complexes are isomorphous and as mentioned in the Supramolecular Motifs section of the II 2+ Introduction (Section 1.4), pairs of [M (phen)3] complexes interact via one OFF and two EF interactions and as such exhibit a P4AE, which propagates to give the phen motif. The results described above suggest that the phen motif is robust enough II 2+ to allow co-crystallisation of multiple different [M (phen)3] complexes (including both first and second row transition metals) at various relative ratios with no apparent

31

CHAPTER 1 selectivity. Thus, for the purpose of crystallisation, the complexes are completely interchangeable as subtle differences between complexes go unnoticed.

In contrast to the fore-going results, the SEM-EDX scatter plot for co-crystals of

[NixRu1-x(bipy)3](PF6)2 is shown in Figure 17. As with the plot shown previously, the data shown in Figure 17 are plotted as the “Mole fraction of Ni complex in solution” versus the “Mole fraction of Ni complex in solid”, where the fraction in solution refers to the relative concentration of [Ni(bipy)3](PF6)2 in solution and the fraction in the solid refers to the x variable in the [NixRu1-x(bipy)3](PF6)2 the co- crystal formula. Once again, the fraction of the ruthenium complex present in the co- crystals was calculated by subtracting the fraction of the nickel complex (x) from one (1-x).

SEM-EDX of [NixRu1-x(bipy)3](PF6)2 series 1.001.00 01.00

0.900.90 00.9.10

0.800.80 00.8.20

in solidin in solidin 0.700.70 00.7.30

0.600.60 00.6.40

0.500.50 00.5.50

0.400.40 00.4.60

0.300.30 00.3.70

0.200.20 00.2.80 Mole fraction of Ni complexNifractionofMole 0.100.10 00.1.90 complex Ru fractionofMole

0.000.00 10.00 0.00 00.10.10 00.20.20 00.30.30 00.40.40 00.50.50 00.60.60 00.70.70 00.80.80 00.90.90 1.00

Mole fraction of Ni complex in solution

Figure 17: Scatter plot and regression line for SEM-EDX analyses of [NixRu1-x(bipy)3](PF6)2 co-crystals. Note that the metal ratios of [NixRu -x(bipy)3](PF6)2 co-crystals harvested from the same solution differ significantly.35

32

CHAPTER 1

The data in Figure 17 are colour-coded. It is important to note that data points of the same colour within any given batch represent measurements obtained from a single co-crystal. For example, three co-crystals were analysed from the batch that contained 40% [Ni(bipy)3](PF6)2 in solution. The data points corresponding to these measurements are enclosed in the black box. The red markers within this box were obtained from a different co-crystal to the points in blue or green (within the box) but that all co-crystals were harvested from the same solution. The colour coding only applies to individual batches and not to the entire series. There is no relationship between the colour codes used for crystals from different co-crystallisation batches.

The data plotted in Figure 17 look very different to the plot obtained for the

[NixRu1-x(phen)3](PF6)20.5H2O series (Figure 16). The SEM-EDX data of

[NixRu1-x(bipy)3](PF6)2 co-crystals illustrated that measurements made from the same co-crystal were very similar (within 2%), but that measurements obtained from different co-crystals grown from the same solution were very different to each other

(such that xsingle co-crystal 1 ≠ xsingle co-crystal 2) and different to the ratio present in solution: i.e. xsolution ≠ xsolid. The scatter plots generated from SEM-EDX data for all other A B A B combinations of [M xM 1-x(bipy)3](PF6)2 (M , M = Fe, Ni, Ru) yielded similar results to those shown in Figure 17.

II II The crystals of pure [M (bipy)3](PF6)2 (M = Fe, Ni, Ru) complexes are isomorphous and as mentioned in the Supramolecular Motifs section of the II 2+ Introduction (Section 1.4), pairs of [M (bipy)3] complexes interact via six EF interactions and as such exhibit a 6AE, which propagates to give the bipy motif. Results from these systems suggested that for the purposes of crystallisation, II 2+ molecules of different [M (bipy)3] complexes are similar enough to co-crystallise but not similar enough that they are completely interchangeable in the crystal packing motif.

To explain these unprecedented results the term supramolecular selection was introduced, which applies to the co-crystallisation of two molecules (A and B), that are chemically and structurally very similar. When A and B are co-crystallising from the same solution, like molecules organise through supramolecular interactions.

33

CHAPTER 1

Interactions of the type A···A and B···B are slightly more favourable than A···B. Consequently, some crystals will nucleate with a higher concentration of A compared to B (and vice versa) relative to the initial A:B ratio in solution. Propagation of crystal growth is then influenced by the ratio of A to B present in the crystal. Crystals richer in A will preferentially select for A over B (through molecular recognition), while those that nucleated with a higher proportion of B will continue to prefer B during co-crystallisation. For both occurrences, the selection process is not exclusive but preferential. Therefore it is possible to yield co-crystals from a solution that contained an equimolar ratio of A and B, where some co-crystals have a higher proportion of A and others have a higher proportion of B.

II 2+ It is therefore very interesting that [M (bipy)3] complexes displayed II 2+ supramolecular selection while the [M (phen)3] complexes showed no supramolecular selection, given that both types of complexes are outwardly very similar (albeit 2,2′-bipyridine ligands are less rigid and slightly smaller than 1,10-phenthroline ligands), engage in similar intermolecular interactions and have the same molecular symmetry (D3). Therefore, co-crystallisation of similar molecules does not, as previously assumed, necessarily result in the formation of co-crystals with the same homogeneous distribution of composition. This is significant revelation, as any measurement performed on bulk samples would only show the average results for the range of co-crystals and their compositional variations. Therefore, it is of high importance that future research concerning the formation of co-crystals includes experiments to determine the relative homogeneity of single co-crystals, prior to drawing conclusions regarding the properties of bulk co-crystalline samples. The work presented within this thesis can be considered as a significant broadening and deepening of the research discussed in this section.

34

CHAPTER 2

CHAPTER 2: Project objectives

2.1 Overall research objectives

The overall objective for this research was to examine co-crystal formation for a range of different metal complexes. The premise behind this research was to engineer new crystalline materials with potentially tunable properties. The synthesis of these novel co-crystalline materials involved the exploitation of known supramolecular motifs and architectures to incorporate known amounts of different metal complexes into single co-crystals. Of interest were: the syntheses of co-crystalline materials that form molecular structures that propagate through the 2D terpy embrace motif; and III 3- those that form framework structures through the polymerisation of [M (ox)3] building-blocks. For example, many of the experiments involved the co-crystallisation of complexes that form non-isomorphous structures in their pure form. These types of experiments provide a methodology for potentially tuning the co-crystalline phase based on the initial concentration of metal complexes in solution i.e. observe if, and at what concentration, one phase is preferred over the other.

The experiment design and aims of this research were multifaceted; however, for each system investigated, the objective was to gain a deeper understanding of crystal engineering and molecular recognition. Specific focus was placed on factors that may affect the ability of metal complexes to engage in molecular recognition for like complexes, such as ligand type and size, mode of intermolecular interaction and whether the complexes form discrete or polymeric structures. These and other factors, and their hypothesised consequent effect on the co-crystallisation process, were to be investigated through various binary homoleptic and different ligand experiments.* By conducting these experiments, it was hoped a better understanding of the limits of co-crystallisation were to be gained. The following subsections outline the more specific research aims for each type of co-crystallisation system that were investigated.

* See footnote on page 76 for clarification regarding the terms homoleptic and different ligand.

35

CHAPTER 2

2.2 Molecular co-crystalline materials

II 2+ During this research several co-crystallisation experiments involving [M (terpyR)2] complexes were performed. The degree of supramolecular selection for each co-crystallisation experiment was investigated by incrementally introducing various differences between the metal complexes that were to be co-crystallised. The extent of supramolecular selection was inferred by examining the degree of compositional variation among resulting co-crystals harvested from the same solution. Co-crystals were to be characterised using techniques such as SEM-EDX, SCXRD and PXRD. A measure of the robustness of a supramolecular motif was how much it could withstand disruption. Overall, the experiments that were performed during this research aimed to study the ability of the terpy motif to endure various degrees of lattice disruption. A detailed introduction into the terpy motif is provided in the Results and Discussion chapter for these experiments (Section 4.1). It was postulated that complexes with greater differences would more readily engage in molecular recognition for like complexes and hence display more supramolecular selection.

The first set of experiments that were performed were homoleptic co-crystallisations, II where [M (terpy)2](PF6)2 complexes were co-crystallised with [Ru(terpy)2](PF6)2, to II II form co-crystals of the general formula [M xRu1-x(terpy)2](PF6)2 (M = Fe, Co, Ni, Cu). Complexes involved are chemically different but geometrically almost indistinguishable from one another. This set of experiments was therefore designed to test the effects of minor differences between complexes on the co-crystallisation process.

II Several co-crystals with the general formula [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (MII = Fe, Ni, Cu) were prepared through different ligand co-crystallisation II experiments, where [M (terpyOH)2](BF4)2 complexes were co-crystallised with

[Ru(terpy)2](BF4)2. Each experiment combination involved complexes that are chemically and structurally different (i.e. different metal centres and ligands) but similar enough to form very similar 2D terpy embrace motifs. These experiments were designed to test the effects of moderate differences between complexes, which are able to form the same motif on co-crystallisation.

36

CHAPTER 2

In addition to these experiments, a co-crystallisation experiment where III [Ru(terpy)2](BF4)2 was co-crystallised with [Co (terpyO)(terpyOH)](BF4)2 was II prepared. Unlike [M (terpyOH)2](BF4)2 metal complexes, which interact through π- III interactions to yield the 2D terpy motif, [Co (terpyO)(terpyOH)](BF4)2 complexes predominately interact through hydrogen bonds (no π-interactions between complexes) to form a hydrogen bond motif. This experiment was designed to test whether co-crystallisation would force [CoIII(terpyO)(terpyOH)]2+ into a non 2+ hydrogen bonding lattice or [Ru(terpy)2] complexes (which cannot form hydrogen bonds) into the hydrogen bond motif.

Another set of different ligand experiments that were performed involved the II II co-crystallisation of [M (terpyPh)2](PF6)2 complexes (M = Fe, Ni, Cu) with

[Ru(terpy)2](PF6)2 complexes. The phenyl ring on the 4′-carbon atom of the terpyPh ligand is much larger than the hydroxyl group and this has been shown to disrupt the II 2+ 2D terpy motif. Nevertheless, [M (terpyPh)2] complex pairs interact through a similar terpy embrace consisting of one OFF and two EF π-interactions. These experiments were designed to test the effects of larger differences between complexes, which are capable of interacting through the same set of π-interactions on co-crystallisation.

The final set of experiments in this section involved the co-crystallisation of

[Ru(terpyR)2](PF6)2 (terpyR = terpy, terpyPh) with either [Ni(phen)2](PF6)2 or II 2+ 2+ [Ni(bipy)2](PF6)2. The main difference between [M (terpy)2] and [Ni(L)3] II 2+ complexes (L = phen, bipy) is that [M (terpy)2] complexes have S4 point 2+ symmetry, while [Ni(L)3] have D3 point symmetry. Regardless of the structural differences, all of the complexes involved in these experiments are of a similar size and form structures by engaging in some combination of OFF and/or EF interactions, albeit forming different motifs. Complexes involved in each co-crystallisation are chemically and structurally different, form different motifs in their pure form but are hypothetically capable of interacting through a compatible set of π-interactions. These experiments tested the effects of pronounced differences between complexes on the co-crystallisation process. It was also of interest to observe which if any motif dominates in the co-crystalline phase.

37

CHAPTER 2

2.3 Metal-organic framework co-crystalline materials

The experiment design for this research component focused on the synthesis of polymeric metal-organic frameworks. During this research a variety of III 3- co-crystallisation and epitaxial experiments involving the [M (ox)3] metal complex building-block were performed. These experiments were designed to test if the enhanced electronic communication between metal centres afforded by the bridging nature and negative charge of the oxalato ligand resulted in greater supramolecular III 3- selection. A detailed introduction into the frameworks containing the [M (ox)3] building-block is provided in the Results and Discussion chapter for these experiments (Section 5.1.1). As with the co-crystals resulting from the molecular systems, the extent of supramolecular selection was inferred by examining the degree of compositional variation among co-crystals that were collected from the same solution. Co-crystals that formed were to be characterised using techniques such as SEM-EDX, SCXRD, PXRD and Raman spectroscopic mapping.

The first set of experiments that were conducted are described as homoleptic anionic metal dilutions. These experiments involved the co-crystallisation of two different III III K3[M (ox)3]·xH2O complexes (M = Mn, Cr, Fe, Ru and Rh) to form co-crystals of A B the general formula K3[M xM 1-x(ox)3]·xH2O. Extensions of these experiments using epitaxial crystallisation methods were also performed. These epitaxial crystallisation experiments involved the immersion of single crystal seeds of the formula III III III [M (ox)3]·2.5H2O (M = Cr, Fe) into saturated solutions of K3[M (ox)3](aq/EtOH) III (M = Cr, Fe or a 1:1 mixture). Crystals containing K3[Cr(ox)3]·2.5H2O complexes are usually very dark green/blue while those containing K3[Fe(ox)3]·2.5H2O complexes are bright green. Analyses of the differences in colour between the seed and epitaxial domains were designed to aid the understanding of the crystal growth A B patterns of K3[M xM 1-x(ox)3]·xH2O that were grown by the co-crystallisation of two III different K3[M (ox)3]·xH2O complexes.

It was also of interest to observe the growth patterns in experiments that involved the simultaneous immersion of K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O seeds into solutions of either K3[Cr(ox)3](aq/EtOH) or K3[Fe(ox)3](aq/EtOH). Experiments where pure

K3[Fe(ox)3]·2.5H2O seed crystals were placed in a saturated solution containing an

38

CHAPTER 2 equimolar ratio of both complexes were also of particular interest. These experiments were designed to test the selection process in systems that contain competing metal complexes. Overall, all of these epitaxial experiments aimed to provide a better A B understanding of the mechanisms driving the formation of K3[M xM 1-x(ox)3]·xH2O co-crystals.

III 3- A total of six experiments that involved the co-crystallisation of [M (ox)3] III II 2+ II (M = Cr, Fe) with [M (L)3] (M = Ni, Ru and L = bipy, phen) in the presence of Na+ were also prepared. Four of these co-crystallisation experiments aimed to form co-crystals of the formula [NixRu1-x(L)3][NaCr(ox)3] and [Ru(L)3][NaFexCr1-x(ox)3] (L = phen or bipy). The remaining two experiments that were prepared aimed to A B A form co-crystals of the general formula [M (bipy)3]x[M (phen)3]1-x[NaCr(ox)3] (M , B II 2+ M = Ni, Ru or vice versa). Experiments that involved the dilution of the [M (L)3] site were designed to test the supramolecular selection in systems where the cationic complexes do not engage in intermolecular interactions with each other.

39

CHAPTER 3

CHAPTER 3: Preparative experimental details and methodology

3.1 Materials

The starting materials 2,2′:6′,2′′-terpyridine (terpy), 2,6-bis(2-pyridyl)-4(1H)-pyridone (terpyOH), 1,10-phenanthroline (phen),

2,2′-bipyridine (bipy), lithium chloride (LiCl), sodium tetrafluoroborate (NaBF4), potassium hexafluorophosphate (KPF6), potassium permanganate (KMnO4), potassium dichromate (K2Cr2O7) and silver nitrate (AgNO3) were purchased from Sigma Aldrich with 98% or higher stated purity and used without any further purification. Iron (II) chloride tetrahydrate (FeCl2·4H2O), iron (III) chloride hexahydrate (FeCl3·6H2O), cobalt (II) chloride hexahydrate (CoCl2·6H2O), nickel (II) chloride hexahydrate (NiCl2·6H2O), copper (II) chloride dihydrate (CuCl2·2H2O), oxalic acid hydrate (H2C2O4·H2O), potassium oxalate dihydrate (K2C2O4·2H2O), potassium carbonate (K2CO3) and potassium hydroxide (KOH) were of reagent grade quality and were purchased from Banksia Scientific. RuCl3·xH2O (x ≈ 3.5) was purchased from Precious Metals Online and had a stated purity of 99%. RhCl3·xH2O (x ≈ 3) was kindly provided by Associate Professor Dennis Arnold. All solvents were of reagent grade quality and used as supplied by the manufacturers.

3.2 Characterisation techniques

3.2.1 Scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX)

Samples were prepared in one of the following ways:

More stable samples were mounted on aluminium stubs using double sided carbon tape as they did not crumble under the vacuum atmosphere of the SEM. Co-crystals A B of the general formula K3(M xM 1-x(ox)3]·xH2O were initially prepared using the carbon tape method but were found to deteriorate rapidly into a powder once under vacuum in the SEM. Instead, these samples were first embedded in a putty adhesive

40

CHAPTER 3 to minimise the surface area exposed and thus give the single crystal more structural support. All co-crystals regardless of the mounting method were then coated with a thin layer of evaporated carbon to enhance surface conductivity and reduce charging.

Energy-Dispersive X-ray (EDX) analysis was conducted on a JEOL 840A analytical scanning electron microscope (SEM) integrated with a JEOL 2300 micro-analyser. Accelerating voltage was set at 20 kV. The electron beam current was set at 1.000 nA, which was measured with a Faraday cup, while the acquisition live time was the same for all samples of the same type and was usually between 20-60 seconds (depending on the stability of the sample), with an average of 2400 counts per second. The instrument was calibrated using a set of standard blocks mounted with natural minerals containing elements found in the samples to be analysed. Prior to every analysis session, samples of known concentrations such as A B A B [M 0.50M 0.50(phen)3](PF6)2 single co-crystals (M and M are the same transition metals as those in the unknown sample) were used as a check of the instrument’s accuracy and precision.261 Atomic percentages were calculated in the JEOL EDS software suite by a standardised quantitative analysis method using a phi-rho-z X-ray depth distribution function with a fitting coefficient no more than 0.10. Appendix A contains a discussion regarding the use of EDX as a technique for elemental analysis. All of the data used throughout this research originated from chemically justifiable data and where this was not possible other avenues of characterisation were explored.

3.2.2 Powder X-ray diffraction (PXRD)

Samples were prepared as thin films on silicon 511 wafers and were analysed at room temperature on instruments equipped with either Cu or Co anodes. X-ray Diffraction (XRD) patterns were collected either using a PANalytical X’Pert PRO X-ray diffractometer (radius of 240 mm) with incident X-ray radiation sourced from a line-focused PW3373/00 copper (Cu) X-ray tube, or with a Philips X-ray diffractometer (radius 173 mm) with an incident X-ray radiation sourced from a line focused PW1050 cobalt (Co) X-ray tube. Both X-ray tubes were used at 40 kV and

40 mA, with Kα wavelengths of 1.54060 Å and 1.78901 Å respectively. For all patterns acquired with Cu radiation, a Bragg–Brentano beam geometry was chosen. Depending on the sample type, starting positions ranged from 3-5° 2θ, while end

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CHAPTER 3 positions were typically to 60-90° 2θ. Step sizes ranged from 0.017-0.020° 2θ, at 2.0-8.0 seconds per step. Data for photosensitive samples (as specified) were collected in the dark to avoid decomposition during analysis. For direct comparison of patterns within a series, all samples within that series were analysed under the same conditions using the same parameters. The experimental patterns were then compared with patterns simulated from experimental refinement data or known structures found in the CSD.51 The X’pert Highscore Plus (PANanalytical) software package was used to analyse the diffraction patterns and to calculate the simulated patterns from single crystal data.

3.2.3 Single crystal X-ray diffraction (SCXRD)

Reflection data were collected using the CrysAlis package on an Oxford Diffraction Xcalibur diffractometer at 173 K equipped with a Sapphire3 Gemini Ultra detector and a graphite monochromator.262 X-ray radiation was from a fine-focused sealed

Molybdenum (Mo) X-ray tube at 40 kV and 50 mA, with a Kα wavelength of 0.71073 Å. The data collection mode (Laue Class, hemisphere, full sphere) and exposure time per frame were determined within the software package, depending on the intensity of diffraction displayed by the crystal and the fit percentage of reflection data to the determined cell in the pre-experiment.

Data reduction was conducted using CrysAlis RED, within which multi-scan empirical absorption corrections were applied using spherical harmonics, implemented in the SCALE3 ABSPACK scaling algorithm.262 Crystal structures were solved via direct methods using SIR97263 and refined with SHELXL97264 through the WINGX graphical user interface.265 Full occupancy non-hydrogen atoms were refined with anisotropic displacement parameters. C-H hydrogen atoms were included in idealised positions and a riding model was used for their refinement. The MA and MB atoms in the co-crystals shared the same sites. Their coordinates and anisotropic displacement parameters (where applicable) were fixed to be equivalent in each case and occupancies were refined to determine an estimate of the relative proportion of each metal in the crystals. Final refinement cycles were done with the relative occupancies fixed at the ratios found. The attached CD contains the crystallographic information files (.cif) for the crystal structures presented herein.

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3.2.4 Nuclear magnetic resonance spectroscopy (NMR)

Most of the compounds discussed in this thesis contain octahedral paramagnetic cations (Co2+, Ni2+, Cu2+, Cr3+, Fe3+) and therefore, NMR spectroscopy was only used for characterisation of the diamagnetic complexes and organic ligands.

1 Samples were prepared in CDCl3, d6-DMSO, d6-acetone or D2O as specified. H NMR spectra were recorded on a Bruker Avance 400 MHz at room temperature. Chemical shifts are reported in ppm and referenced against the relevant solvent peak.

3.2.5 High resolution electrospray ionisation mass spectrometry (ESI-MS)

Electrospray ionisation mass spectrometry was conducted on an Agilent 6520 Accurate-Mass Q-TOF LC/MS. Samples were dissolved in HPLC grade solvents and diluted to concentrations of 10 µg·cm-3. Ultra-pure nitrogen gas was used as both the drying and nebulising gas and the source temperature was set to 350°C. The fragmentor and skimmer voltages were set at 100 V and 20 V respectively (unless otherwise specified). Mass spectra were collected in both positive and negative ion modes (as specified) from m/z 100 to 1000 Da.

3.2.6 Raman spectroscopy

Powders of the samples were placed directly on a polished metal slide while single crystals were affixed to a glass slide with putty adhesive to ensure a flat and level surface. The slides were then placed on the stage of an Olympus BHSM microscope fitted with a 50× long working distance objective. Analysis was performed on a Renishaw 1000 Raman microscope system equipped with a monochromator, a notch filter system, a thermo-electrically cooled Charge Coupled Device (CCD) detector and a Spectra-Physics model 127 Nd-YAG laser (785 nm). Raman spectra were acquired in the range between 100-2000 cm-1. Spectra were calibrated using the 520.5 cm-1 line of a silicon wafer prior to every analysis session and then with the -1 1722.97 and 1727.47 cm carbonyl stretching bands of pure K3[Fe(ox)3]·2.5H2O and

K3[Cr(ox)3]·2.5H2O single crystals respectively.

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Single crystal Raman spectroscopic mapping was used to map the change in the carbonyl stretching frequency at different locations on K3(CrxFe1-x(ox)3]·xH2O single co-crystals. Raman line maps were measured along transects that spanned the single crystal surface while area maps were measured so that the maximum possible area of the selected surface of each individual crystal was analysed. Confocal experiments were measured to depths of up to 500 µm; however, the signal to noise intensity at these depths was at times very poor. Raman spectra collected during mapping were acquired in the range between 1300-1800 cm-1. All maps were conducted with the aid of a computer controlled automatic stage. Spectral processing, such as curve fitting, was performed using the WiRE Raman Renishaw software package.

3.2.7 Elemental analysis

Elemental microanalysis (C, H, N) was performed by the University of Queensland Microanalytical Service. Difference calculations were employed to determine the solvate species. For crystals that desolvate readily, microanalysis was carried out after the crystals were air-dried.

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3.3 Synthetic experimental details

The terpyPh ligand and metal complexes studied in this work were synthesised and crystallised using reported literature procedures. The ligands, precursors and complexes are indexed in Table 3.

Table 3: Compound index

Section Formula Section Formula

3.3.1 terpyPh 3.3.2.16 [Ru(terpy)2](BF4)2·H2O

3.3.2.1 [Fe(terpy)2](PF6)2 3.3.2.17 [Ru(terpyPh)2](PF6)2·4MeCN

3.3.2.2 [Co(terpy)2](PF6)2 3.3.2.18 [Ru(terpyOH)2](BF4)2·H2O

3.3.2.3 [Ni(terpy)2](PF6)2 3.3.3.1 [Ni(phen)3]Cl2·8.5H2O

3.3.2.4 [Cu(terpy)2](PF6)2 3.3.3.2 [Ni(phen)3](PF6)2·H2O

3.3.2.5 [Fe(terpyPh)2](PF6)2·MeCN·H2O 3.3.3.3 [Ni(bipy)3]Cl2·7H2O

3.3.2.6 [Ni(terpyPh)2](PF6)2·4MeCN 3.3.3.4 [Ni(bipy)3](PF6)2

3.3.2.7 [Cu(terpyPh)2](PF6)2·4MeCN 3.3.3.5 cis-[Ru(phen)2Cl2]·2H2O

3.3.2.8 [Fe(terpyOH)2](BF4)2·H2O 3.3.3.6 cis-[Ru(bipy)2Cl2]·2H2O

3.3.2.9 [Ni(terpyOH)2](BF4)2·H2O 3.3.3.7 [Ru(phen)3]Cl2·9H2O

3.3.2.10 [Cu(terpyOH)2](BF4)2·H2O 3.3.3.8 [Ru(bipy)3]Cl2·7H2O

3.3.2.11 [Co(terpyOH)(terpyO)](BF4)2·3.5H2O 3.3.4.1 K3[Mn(ox)3] ·xH2O

3.3.2.12 cis-[Ru(DMSO)4Cl2] 3.3.4.2 K3[Cr(ox)3]·2.5H2O

3.3.2.13 [Ru(terpy)Cl3] 3.3.4.3 K3[Fe(ox)3]·2.5H2O

3.3.2.14 [Ru(terpy)2]Cl2 3.3.4.4, 3.3.3.5 K3[Ru(ox)3] ·xH2O methods 1 and 2

3.3.2.15 [Ru(terpy)2](PF6)2 3.3.4.6 K3[Rh(ox)3]·2H2O

3.3.1 Synthesis of 4′-phenyl-2,2′:6′,2′′-terpyridine (terpyPh)

3.3.1.1 3-phenyl-1,5-bis(2-pyridyl)-1,5-pentanedione

This precursor was synthesised by the literature method of Constable et al.266 The compound 2-acetylpyridine (5.0 cm3, 44.6 mmol) was added dropwise to a stirred emulsion of benzaldehyde (2.3 cm3, 22.6 mmol) in EtOH (20 cm3) and aqueous sodium hydroxide solution (15 cm3, 1.5 M, 22.5 mmol). After addition of approximately 10 drops of the 2-acetylpyridine, a white precipitate was observed. This precipitate continued to form during the addition of the remaining

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2-acetylpyridine as the solution changed colour from a tan brown to vibrant orange. The mixture was left to stir for 24 hours in air at room temperature (ca. 28°C). The fine white solid produced was collected by vacuum filtration and washed with cold 3 3 EtOH (3 × 5.0 cm portions) and then cold H2O (3 × 10 cm portions) and air dried. The product was then recrystallised from a warmed 1:2 mixture of DMF and EtOH to give colourless crystals. Yield: 5.713 g (78%). The compound was not characterised but used immediately in the following step.

3.3.1.2 4′-Phenyl-2,2′:6′,2′′-terpyridine (terpyPh)

N N N Figure 18: 4′-Phenyl-2,2′:6′,2′′-terpyridine (terpyPh)

The ligand shown in Figure 18 was synthesised via a modification of the method published in the literature.94,266-268 The compound 3-phenyl-1,5-bis(2-pyridyl)-1,5- pentanedione (Section 3.3.1.1, 4.956 g, 15.0 mmol) and ammonium acetate (5.010 g, 65.0 mmol) were stirred overnight at reflux in EtOH (75 cm3). During this time, the solution changed colour from colourless to bright yellow. After allowing the reaction mixture to settle, a small amount of white solid (most likely unreacted precursor) was observed at the base of the flask. The solid was removed by hot filtration through fluted filter paper and the yellow/green filtrate was reduced to ca. 50% of its initial volume in vacuo. The mixture was left to cool to room temperature overnight in a round-bottomed flask covered in aluminium foil, during which time yellow needles began to crystallise out of the bright green solution. The flask was then stoppered and placed in a freezer (ca. -20°C) for 2 days before collecting the yellow crystalline product by vacuum filtration and washing with cold EtOH (2 × 5 cm3), then cold 3 H2O (3 × 10 cm ). After recrystallisation from a minimum volume of boiling EtOH, the yellow, crystalline product was collected by vacuum filtration, placed in a glass vial, wrapped in aluminium foil, dried and stored in vacuo over silica gel. Yield 1.704 g (37%). m.p 209-211°C Mass spectrum: (HR-ESI) MeOH [L + H]+ m/z + 1 310.1357 [60%] (calculated for [C21H16N3] , 310.1344). H-NMR Spectrum: δH (400

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3 3 MHz; CDCl3) 8.74 (s, 2H), 8.73 (unresolved dd, JHH = 4.4 Hz, 2H), 8.68 (d, JHH = 3 4 3 8.2 Hz, 2H), 7.91 (dd, JHH = 8.2 Hz, JHH = 1.2 Hz, 2H), 7.87 (dd, JHH = 7.6 Hz, 4 3 4 JHH = 1.8 Hz, 2H), 7.52 (tt, JHH = 7.6 Hz, JHH = 1.8 Hz, 2H), 7.45 (unresolved tt, 3 3 4 JHH = 7.64 Hz, 1H), 7.36 (ddd, JHH = 7.6 Hz, JHH = 1.2 Hz, 2H). This is a match to reported literature values.266

II 3.3.2 Synthesis of [M (L)2]X2 transition metal complexes

These complexes, all of which have been previously reported, were synthesised using modified literature procedures.32-34,266,269-275 Complexes of the formula II II II II [M (terpy)2](PF6)2, [M (terpyOH)2](BF4)2 and [M (terpyPh)2](PF6)2 (M = Fe, Co, Ni, Cu) were all prepared using similar procedures, however the syntheses of II [M (terpyPh)2](PF6)2 complexes were conducted in the dark. In each case, the ligand (ca. 1 mmol) was dissolved in warm EtOH or MeOH (ca. 5 cm3, at ca. 40°C) and added dropwise to a warmed aqueous solution of the appropriate metal(II) chloride (ca. 0.5 mmol in 5 cm3 at ca. 40°C). The ligand was added in slight excess to the metal ion (ca. 2.1:1) in order to ensure a slightly basic environment and to complete complexation of the metal ions. During the addition of all the ligand solutions, a colour change was observed and this is documented in the corresponding experimental sections. The complexes were then precipitated via metathesis with saturated aqueous solutions of either KPF6 and NaBF4 salts and then filtered using a sintered glass funnel, and washed with cold H2O until a sample of the filtrate remained clear when reacted with aqueous AgNO3 (ca. 1.0 M). Unless otherwise II specified, [M (L)2]X2 complexes were recrystallised from 1:1 MeCN:H2O solvent mixtures using the solvent evaporation method.

3.3.2.1 [Fe(terpy)2](PF6)2

A solution of 2,2′:6′,2′′-terpyridine (0.244 g, 1.05 mmol) in EtOH (5 cm3 at ca. 40°C) was added dropwise to FeCl2·4H2O (0.099 g, 0.499 mmol) dissolved in H2O (ca. 5 cm3 at 40°C). During the addition of the ligand solution, the reaction mixture changed colour from yellow to brown and then finally to deep violet. A saturated aqueous solution of KPF6 (5 drops) was added immediately, resulting in a purple precipitate. The solid was filtered and recrystallised to produce thin dark purple

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2+ rectangular crystals. Yield 0.366 g (91%). Mass spectrum: (HR-ESI) MeCN [ML2] 2+ + m/z 261.0649 [100%] (calculated for [C30H22N6Fe1] , 261.0628), [ML2 + X] m/z + 1 667.0913 [39%] (calculated for [C30H22N6Fe1 + PF6] , 667.0898). H-NMR 3 Spectrum: δH (400 MHz; d6-DMSO) 9.22 (d, JHH = 7.6 Hz, 4H), 8.79 (unresolved m, 3 6H), 7.99 (t, JHH = 7.6 Hz, 4H), 7.16 (unresolved m, 8H). The peaks are broad, presumably due to the large amount of water present as indicated by the peak at 3.42 ppm.

3.3.2.2 [Co(terpy)2](PF6)2

A solution of 2,2′:6′,2′′-terpyridine (0.239 g, 1.025 mmol) in EtOH (5 cm3 at ca.

40°C) was added dropwise to CoCl2·6H2O (0.116 g, 0.488 mmol) dissolved in H2O (ca. 5 cm3 at 40°C). During the addition of the ligand solution, the reaction mixture changed colour from pink to dark orange and then finally to brown. Addition of saturated aqueous KPF6 solution (5 drops) resulted in a tan precipitate. The solid was filtered and recrystallised to produce thin brown rectangular crystals. Yield 0.354 g 2+ (89%). Mass spectrum: (HR-ESI) MeCN [ML2] m/z 262.5639 [100%] (calculated 2+ + for [C30H22N6Co1] , 262.5619), [ML2 + X] m/z 670.0889 [29%] (calculated for + [C30H22N6Co1 + PF6] , 667.0880).

3.3.2.3 [Ni(terpy)2](PF6)2

A solution of 2,2′:6′,2′′-terpyridine (0.233 g, 1.00 mmol) in EtOH (5 cm3 at ca. 40°C) was added dropwise to NiCl2·6H2O (0.112 g, 0.476 mmol) dissolved in H2O (ca. 5 cm3 at 40°C). During the addition of the ligand solution the reaction mixture changed colour from pale green to tan and then finally to light brown. Addition of saturated aqueous KPF6 solution (5 drops) resulted in a light brown precipitate. The solid was filtered and recrystallised to produce thin light brown square crystals. Yield 0.349 g 2+ (90%). Mass spectrum: (HR-ESI) MeCN [ML2] m/z 262.0646 [100%] (calculated 2+ + for [C30H22N6Ni1] , 262.0630), [ML2 + X] m/z 669.0910 [46%] (calculated for + [C30H22N6Ni1 + PF6] , 669.0901).

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3.3.2.4 [Cu(terpy)2](PF6)2

A solution of 2,2′:6′,2′′-terpyridine (0.233 g, 0.997 mmol) in EtOH (5 cm3 at ca.

40°C) was added dropwise to CuCl2·2H2O (0.081 g, 0.475 mmol) dissolved in warm 3 H2O (ca. 5 cm at 40°C). During the addition of the ligand solution the reaction mixture changed colour from light blue to blue and then finally to dark blue.

Addition of saturated aqueous KPF6 solution (5 drops) resulted in a light blue/green precipitate. The solid was filtered and recrystallised to produce thin blue/green rectangular shaped crystals. Yield 0.354 g (91%). Mass spectrum: (HR-ESI) MeCN 2+ 2+ [ML2 + H] m/z 265.0854 [100%] (calculated for [C30H23N6Cu1] , 265.0640). This base peak in the ESI-MS for the protonated yet dicationic ion indicates that the Cu2+ complex is very easily prone to reduction under the conditions of the mass spectrometer to a Cu+ complex ion.

3.3.2.5 [Fe(terpyPh)2](PF6)2·MeCN·H2O

A solution of 4′-phenyl-2,2′:6′,2′′-terpyridine (Section 3.3.1.2, 0.190 g, 0.613 mmol) 3 in EtOH (5 cm at ca. 40°C) was added dropwise to FeCl2·4H2O (0.058 g, 3 0.292 mmol) dissolved in warm H2O (ca. 5 cm at 40°C). During the addition of the ligand solution the reaction mixture changed colour from yellow to brown and then finally to deep violet. A saturated aqueous solution of KPF6 (5 drops) was then added, immediately resulting in an intense purple precipitate. The solid was filtered and recrystallised to produce dark purple long rectangular crystals. After 15-30 minutes out of the mother liquor the crystals began to desolvate and appeared to lose lustre and eventually formed a powder; this indicates that they likely contain volatile solvents of crystallisation. Yield 0.269 g (90%). Mass spectrum: (HR-ESI) MeCN 2+ 2+ [ML2] m/z 337.0956 [100%] (calculated for [C42H30N6Fe1] , 337.0941), [ML2 + + + 1 X] m/z 819.1515 [27%] (calculated for [C42H30N6Fe1 + PF6] , 819.1523). H-NMR 3 Spectrum: δH (400 MHz; d6-DMSO) 9.69 (s, 4H), 9.08 (d, JHH = 8.2 Hz, 4H), 8.57 3 3 3 (d, JHH = 7.6 Hz, 4H), 8.05 (t, JHH = 7.6 Hz, 4H), 7.85 (t, JHH = 7.6 Hz, 4H), 7.75 3 3 3 (t, JHH = 7.0 Hz, 2H), 7.30 (d, JHH = 5.3 Hz, 4H), 7.21 (t, JHH = 7.0 Hz, 4H).

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3.3.2.6 [Ni(terpyPh)2](PF6)2·4MeCN

A solution of 4′-phenyl-2,2′:6′,2′′-terpyridine (Section 3.3.1.2, 0.191 g, 0.617 mmol) 3 in EtOH (5 cm at ca. 40°C) was added dropwise to NiCl2·6H2O (0.070 g, 3 0.294 mmol) dissolved in warm H2O (ca. 5 cm at 40°C). During the addition of the ligand solution, the reaction mixture changed colour from pale green to deep orange then finally to brown. A saturated aqueous solution of KPF6 (5 drops) was then added immediately resulting in a dark tan precipitate. The solid was filtered and recrystallised to produce tan brown crystals. After no more than 5 minutes out of the mother liquor, the crystals began to desolvate, appeared to lose lustre, and eventually 2+ formed a powder. Yield 0.306 g (92%). Mass spectrum: (HR-ESI) MeCN [ML2] 2+ + m/z 338.0956 [100%] (calculated for [C42H30N6Ni1] , 338.0943), [ML2 + X] m/z + 821.1510 [44%] (calculated for [C42H30N6Ni1 + PF6] , 821.1527).

3.3.2.7 [Cu(terpyPh)2](PF6)2·4MeCN

A solution of 4′-phenyl-2,2′:6′,2′′-terpyridine (Section 3.3.1.2, 0.190 g, 0.616 mmol) 3 in EtOH (5 cm at ca. 40°C) was added dropwise to CuCl2·2H2O (0.050 g, 3 0.293 mmol) dissolved in warm H2O (ca. 5 cm at 40°C). During the addition of the ligand solution the reaction mixture changed colour from pale blue to blue/green and then finally to dark blue/green. A saturated aqueous solution of KPF6 (5 drops) was added immediately, resulting in an intense purple precipitate. The solid was filtered and recrystallised to produce blue/green crystals. After 5 minutes out of the mother liquor, the crystals began to desolvate, appeared to lose lustre, and eventually formed 2+ a powder. Yield 0.310 g (93%). Mass spectrum: (HR-ESI) MeCN [ML2] m/z 2+ 2+ 340.5927 [34%] (calculated for [C42H30N6Cu1] , 340.5914), [M(L)(L + H)] m/z 2+ + 341.0940 [19%] (calculated for [C42H31N6Cu1] , 341.0948), [ML2] m/z 681.1822 + [4%] (calculated for [C42H30N6Cu1] , 681.1817).

3.3.2.8 [Fe(terpyOH)2](BF4)2·H2O

A solution of 2,6-bis(2-pyridyl)-4(1H)-pyridone (0.086 g, 0.343 mmol) in EtOH (5 3 cm at ca. 40°C) was added dropwise to FeCl2·4H2O (0.033 g, 0.163 mmol) 3 dissolved in warm H2O (ca. 5 cm at 40°C). During the addition of the ligand

50

CHAPTER 3 solution the reaction mixture changed colour from yellow to brown and then finally to deep violet. Addition of saturated aqueous NaBF4 solution (10 drops) resulted in a purple precipitate. The solid was filtered and recrystallised to produce purple 2+ crystals. Yield 0.121 g (91%). Mass spectrum: (HR-ESI) MeCN [ML2] m/z 2+ + 277.0588 [100%] (calculated for [C30H22N6O2Fe1] , 277.0577), [M(L)(L – H)] m/z + 1 553.1075 [46%] (calculated for [C30H21N6O2Fe1] , 553.1076). H-NMR Spectrum: 3 3 δH (400 MHz; d6-DMSO) 8.63 (d, JHH = 8.2 Hz, 4H), 8.55 (s, 4H), 7.95 (t, JHH = 3 3 7.6 Hz, 4H), 7.25 (d, JHH = 5.3 Hz, 4H), 7.19 (t, JHH = 6.4 Hz, 4H). The peaks were broad and the phenolic proton was not observed, presumably due to the large amount of water present as indicated by the peak at 3.38 ppm. The NMR spectrum of this compound has not previously been reported.

3.3.2.9 [Ni(terpyOH)2](BF4)2·H2O

A solution of 2,6-bis(2-pyridyl)-4(1H)-pyridone (0.085 g, 0.342 mmol) in EtOH (5 3 cm at ca. 40°C) was added dropwise to NiCl2·6H2O (0.038 g, 0.163 mmol) 3 dissolved in warm H2O (ca. 5 cm at 40°C). During the addition of the ligand solution the reaction mixture changed colour from pale green to tan orange and then finally to brown. Addition of saturated aqueous NaBF4 solution (10 drops) resulted in a brown precipitate. The solid was filtered and recrystallised to produce small brown 2+ crystals. Yield 0.110 g (93%). Mass spectrum: (HR-ESI) MeCN [ML2] m/z 2+ + 278.0594 [100%] (calculated for [C30H22N6O2Ni1] , 278.0579), [M(L)(L – H)] m/z + 555.1083 [60%] (calculated for [C30H21N6O2Ni1] , 555.1079).

3.3.2.10 [Cu(terpyOH)2](BF4)2·H2O

A solution of 2,6-bis(2-pyridyl)-4(1H)-pyridone (0.086 g, 0.344 mmol) in EtOH (5 3 cm at ca. 40°C) was added dropwise to CuCl2·2H2O (0.028 g, 0.164 mmol) 3 dissolved in warm H2O (ca. 5 cm at 40°C). During the addition of the ligand solution the reaction mixture changed colour from pale blue to blue/green and then finally to dark blue/green. Addition of saturated aqueous NaBF4 solution (10 drops) resulted in a brown precipitate. The solid was filtered and recrystallised to produce blue/green rectangular crystals. Yield 0.116 g (94%). Mass spectrum: (HR-ESI)

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2+ 2+ MeCN [ML2] m/z 280.5561 [100%] (calculated for [C30H22N6O2Cu1] , 280.5550), + + [M(L)(L – H)] m/z 560.1020 [74%] (calculated for [C30H21N6O2Cu1] , 560.1022).

3.3.2.11 [Co(terpyOH)(terpyO)](BF4)2·3.5H2O

A solution of 2,6-bis(2-pyridyl)-4(1H)-pyridone (0.076 g, 0.315 mmol) in MeOH (5 3 cm at ca. 40°C) was added dropwise to CoCl2·6H2O (0.036 g, 0.150 mmol) 3 dissolved in warm H2O (ca. 5 cm at 40°C). During the addition of the ligand solution the reaction mixture changed colour from pink to rose brown and then finally to dark red/brown. Air was then vigorously bubbled through the solution for 1 hour. Addition of saturated aqueous NaBF4 solution (20 drops) resulted in a red/brown precipitate. The solid was filtered and recrystallised to produce small red/brown multifaceted crystals. Yield 0.105 g (88%). Mass spectrum: (HR-ESI) + + MeCN [M(L – H)2] m/z 555.0983 [100%] (calculated for [C30H20N6O2Co1] , 1 3 555.0980). H-NMR Spectrum: δH (400 MHz; d6-DMSO) 8.63 (d, JHH = 7.6 Hz, 3 4 3 4H), 8.19 (dt, JHH = 7.6 Hz, JHH = 1.2 Hz, 4H), 8.04 (s, 4H), 7.54 (d, JHH = 5.9 Hz , 3 4 4H), 7.45 (dt, JHH = 6.8 Hz, JHH = 1.2 Hz, 4H). The phenolic proton was not observed, presumably due to the large amount of water present as indicated by the peak at 3.36 ppm. The NMR spectrum of this compound has not previously been reported.

3.3.2.12 cis-[Ru(DMSO)4Cl2]

3 The compound RuCl3·xH2O (2.002 g, 7.40 mmol for x = 3.5) in DMSO (15 cm ) was first purged with N2 gas for 15 minutes then heated at reflux (ca. 160°C) for 10 mins under a N2 atmosphere. During this time, dimethyl sulfide distillate was collected and the reaction mixture changed colour from black/brown to deep red/brown. The solution was slowly cooled to room temperature then placed in an ice bath. Acetone (200 cm3) was then quickly added and the resulting mixture left to cool in an ice bath for a further 20 minutes, during which time a fine yellow product precipitated. The flask was stoppered and placed in the freezer overnight then the solid was filtered, washed with cold acetone (3 × 25 cm3) and dried in vacuo over silica gel. Yield 2.923 g (68%). This complex was used as a synthetic precursor without further purification and was not characterised.

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3.3.2.13 [Ru(terpy)Cl3]

The compound RuCl3·xH2O (0.677 g, 2.50 mmol for x = 3.5) and 2,2′:6′,2′′-terpyridine (0.601 g, 2.57 mmol) in EtOH (60 cm3) were heated at reflux with stirring for 90 minutes. The reaction mixture was allowed to cool slowly to room temperature during which time a fine brown precipitate formed. The black/brown solid was isolated via vacuum filtration and washed with H2O (3 × 20 3 3 3 cm ), EtOH (3 × 20 cm ) and finally Et2O (3 × 20 cm ) then left to dry. Yield 0.987 g (90%). This complex was used as a synthetic precursor without further purification and was not characterised.

3.3.2.14 [Ru(terpy)2]Cl2

The compounds [Ru(terpy)Cl3] (Section 3.3.2.13, 0.657 g, 1.49 mmol), 2,2′:6′,2′′-terpyridine (0.362, 1.55 mmol) and N-ethylmorpholine (17 drops) were added together in EtOH (33 cm3) and heated at reflux. After 3.5 hours the reaction mixture had changed from dark brown to bright red and then was diluted with H2O (30 cm3) and filtered through a pad of Celite®. Most of the EtOH was removed in vacuo and the resulting aqueous solution was split into two (without further purification or characterisation) in preparation for anion exchange (Sections 3.3.2.15 and 3.3.2.16).

3.3.2.15 [Ru(terpy)2](PF6)2

A saturated aqueous solution of KPF6 (20 drops) was added to a solution of 3 [Ru(terpy)2]Cl2 (ca. 15 cm ), which immediately resulted in a bright red precipitate. 3 3 The solid was filtered washed with H2O (2 × 4.0 cm ), cold EtOH (2 × 4.0 cm ) and 3 Et2O (4 × 7.5 cm ). The dried solid was recrystallised to give deep red multifaceted thin prisms. Yield 0.575 g (90% based on half of the [Ru(terpy)Cl3] used in Section 2+ 3.3.2.14). Mass spectrum: (HR-ESI) MeCN [ML2] m/z 284.0486 [100%] 2+ + (calculated for [C30H22N6Ru1] , 284.0479), [ML2 + X] m/z 713.0586 [50%] + 1 (calculated for [C30H22N6Ru1 + PF6] , 713.0599). H-NMR Spectrum: δH (400 MHz; 3 3 3 d6-acetone) 9.08 (d, JHH = 8.2 Hz, 4H), 8.81 (d, JHH = 8.2 Hz, 4H), 8.59 (t, JHH = 3 4 3 7.6 Hz, 2H), 8.08 (dt, JHH = 8.2 Hz, JHH = 1.2 Hz, 4H), 7.70 (d, JHH = 8.2 Hz, 4H),

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3 4 7.33 (ddd, JHH = 7.6 Hz, JHH = 1.2 Hz 4H),. The collected spectrum is a match to literature values.276

3.3.2.16 [Ru(terpy)2](BF4)2·H2O

A saturated aqueous solution of NaBF4 (30 drops) was added to a solution of 3 [Ru(terpy)2]Cl2 (ca. 15 cm ), resulting in a bright red precipitate. The solid was 3 3 filtered and washed with H2O (1 × 2.5 cm ), cold EtOH (2 × 2.5 cm ) and Et2O (4 × 5 cm3). The dried solid was recrystallised to give deep red multifaceted prisms. Yield

0.498 g (88% based on half of the [Ru(terpy)Cl3] used in Section 3.3.2.14). Mass 2+ spectrum: (HR-ESI) MeCN [ML2] m/z 284.0488 [100%] (calculated for 2+ + [C30H22N6Ru1] , 284.0479), [ML2 + X] m/z 655.0985 [45%] (calculated for + 1 [C30H22N6Ru1 + BF4] , 655.0991). H-NMR Spectrum: δH (400 MHz; d6-acetone) 3 3 3 9.10 (d, JHH = 7.6 Hz, 4H), 8.83 (d, JHH = 8.2 Hz, 4H), 8.58 (t, JHH = 8.2 Hz, 2H), 3 4 3 8.07 (dt, JHH = 7.6 Hz, JHH = 1.2 Hz, 4H), 7.71 (d, JHH = 4.7 Hz, 4H), 7.33 (dt,

3 4 277 JHH = 7.6 Hz, JHH = 1.2 Hz, 4H), which is a match to literature values.

3.3.2.17 [Ru(terpyPh)2](PF6)2·4MeCN

The compound 4′-phenyl-2,2′:6′,2′′-terpyridine (Section 3.3.1.2, 0.145 g, 0.483 mmol) dissolved in EtOH (5.5 cm3) was added to a solution of 3 cis-[Ru(DMSO)4Cl2] (Section 3.3.2.12, 0.112 g, 0.230 mmol) in H2O (5.5 cm ). The resulting mixture was heated at reflux with stirring and after 1.5 hours, the solution had changed colour from yellow to deep red. After a total of 4 hours heating at reflux, the reaction was left to cool to room temperature. Precipitation of a bright red solid was achieved through metathesis with a saturated aqueous solution of KPF6 (45 drops). The solid was collected via vacuum filtration, washed with cold EtOH (2 × 5 3 3 cm ) and Et2O (2 × 10 cm ) and recrystallised to give thin red crystals. After 15-30 minutes out of the mother liquor, the crystals began to desolvate, appeared to lose lustre, and eventually formed a powder. Yield 0.195 g (84%). Mass spectrum: 2+ 2+ (HR-ESI) MeCN [ML2] m/z 360.0807 [100%] (calculated for [C42H30N6Ru1] , + + 360.0794), [ML2 + X] m/z 865.1206 [43%] (calculated for [C42H30N6Ru1 + PF6] , 1 3 865.1229). H-NMR Spectrum: δH (400 MHz; d6-acetone) 9.45 (s, 4H), 9.08 (d, JHH 3 4 3 = 8.2 Hz, 4H), 8.34 (dd, JHH = 8.2 Hz, JHH = 1.2 Hz, 4H), 8.12 (dt, JHH = 7.6 Hz,

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4 3 3 JHH = 1.2 Hz, 4H), 7.84 (d, JHH = 5.3 Hz, 4H), 7.77 (t, JHH = 7.6 Hz, 4H), 7.70 (t, 3 3 4 JHH = 7.6 Hz, 2H), 7.36 (dt, JHH = 7.6 Hz, JHH = 1.2 Hz, 4H).

3.3.2.18 [Ru(terpyOH)2](BF4)2·H2O

The compound 2,6-bis(2-pyridyl)-4(1H)-pyridone (0.109 g, 0.438 mmol) in EtOH 3 (5.5 cm ) was added to a solution of cis-[Ru(DMSO)4Cl2] (Section 3.3.2.12, 0.106 g, 3 0.218 mmol) in H2O (5.5 cm ). The resulting mixture was heated at reflux with stirring and after 1.5 hours, the solution had changed colour from yellow to ruby red. After a total of 3.5 hours, heating at reflux the reaction was left to cool to room temperature. Precipitation of a bright red solid was achieved through metathesis with a saturated aqueous solution of NaBF4 (30 drops). The solid was collected via 3 3 vacuum filtration, washed with cold EtOH (2 × 5 cm ) and Et2O (2 × 10 cm ) and recrystallised to give red crystals. Yield 0.141 g (82%). Mass spectrum: (HR-ESI) 2+ 2+ MeCN [ML2] m/z 300.0437 [50%] (calculated for [C30H22N6O2Ru1] , 300.0428), + + [M(L)(L – H)] m/z 599.0763 [27%] (calculated for [C30H21N6O2Ru1] , 599.0778). 1 3 H-NMR Spectrum: δH (400 MHz; d6-acetone) 8.68 (d, JHH = 8.2 Hz, 4H), 8.50 (s, 3 3 3 4H), 8.03 (t, JHH = 8.2 Hz, 4H), 7.76 (d, JHH = 5.9 Hz, 4H), 7.32 (t, JHH = 6.5 Hz, 4H). The phenolic proton was not observed, presumably due to the large amount of water present as indicated by the peak at 2.85 ppm.

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II 3.3.3 Synthesis of [M (L)3]X2 transition metal complexes

These following complexes, all of which have been previously reported, were synthesised using modified literature procedures.

3.3.3.1 [Ni(phen)3]Cl2·8.5H2O

- The synthesis of this complex and subsequent PF6 salt metathesis (Section 3.3.3.2) followed a published literature procedure.278-280 A solution of 1,10-phenanthroline (0.183 g, 1.02 mmol) in EtOH (5 cm3 at ca. 40°C) was added dropwise to 3 NiCl2·6H2O (0.078 g, 0.328 mmol) dissolved in warm H2O (ca. 5 cm at 40°C). During the addition of the ligand solution the reaction mixture changed colour from pale green to purple and then finally to pink. The solvents were removed in vacuo until only solid was visible and the reaction vessel left unstoppered in an oven at ca. 60°C for 1 hour to ensure complete solvent evaporation. An aqueous solution of the crude mixture was then triturated with acetone (ca. 5 cm3) and the solid filtered and washed with cold acetone (2 × 2 cm3). The solid was recrystallised by vapour diffusion of acetone into H2O to give deep pink thin prisms. Yield 0.232 g (86%). 2+ Mass spectrum: (HR-ESI) MeCN [ML3] m/z 299.0732 [100%] (calculated for 2+ + [C36H24N6Ni1] , 299.0708), [ML2 + X] m/z 453.0423 [23%] (calculated for + [C24H16N4Ni1 + Cl] , 453.0417). Elemental Analysis Found: C, 52.51; H, 4.67; N,

10.10. Calculated for C36H41Cl2N6Ni1O8.5: C, 52.52; H, 5.02; N, 10.21.

3.3.3.2 [Ni(phen)3](PF6)2·H2O

An aqueous/ethanolic solution of the complex [Ni(phen)3]Cl2 was synthesised as per the procedure described in Section 3.3.3.1. Saturated aqueous KPF6 (15 drops) was then added which immediately resulted in a pale pink precipitate. The solid was 3 filtered washed with H2O (3 × 5.0 cm ) and left to air dry. The dried solid was recrystallised from a 1:1 acetone:H2O solvent mixture to give deep pink prisms. Yield 2+ 0.268 g (91%). Mass spectrum: (HR-ESI) MeCN [ML3] m/z 299.0715 [100%] 2+ + (calculated for [C36H24N6Ni1] , 299.0708), [ML3 + X] m/z 743.1063 [35%] + (calculated for [C36H24N6Ni1 + PF6] , 743.1063).

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3.3.3.3 [Ni(bipy)3]Cl2·7H2O

- The synthesis of this complex and subsequent PF6 salt metathesis (Section 3.3.3.4) followed a published literature procedure.278-280 A solution of 2,2′-bipyridine (0.157 g, 3 1.01 mmol) in EtOH (5 cm at ca. 40°C) was added dropwise to NiCl2·6H2O 3 (0.077 g, 0.325 mmol) dissolved in warm H2O (ca. 5 cm at 40°C). During the addition of the ligand solution the reaction mixture changed colour from pale green to purple and then finally to orange/pink. The solvents were removed in vacuo until only solid was visible and the reaction vessel then left unstoppered in an oven at ca. 60°C for 1 hour to ensure complete solvent evaporation. An aqueous solution of the crude product mixture was then triturated with acetone (ca. 5 cm3) and the solid filtered and washed with cold acetone (2 × 2 cm3). The solid was recrystallised by vapour diffusion of acetone into H2O to give pink multifaceted prisms. Yield 0.209 g 2+ (89%). Mass spectrum: (HR-ESI) MeCN [ML3] m/z 263.0735 [100%] (calculated 2+ + for [C30H24N6Ni1] , 263.0703), [ML2 + X] m/z 405.0423 [27%] (calculated for + [C20H16N4Ni1 + Cl] , 405.0417). Elemental Analysis Found: C, 49.88; H, 5.10; N,

11.58. Calculated for C30H38Cl2N6Ni1O7: C, 49.75; H, 5.29; N, 11.60.

3.3.3.4 [Ni(bipy)3](PF6)2

An aqueous/ethanolic solution of the complex [Ni(bipy)3]Cl2 was synthesised as per

280 the procedure described in Section 3.3.3.3. Saturated aqueous KPF6 (20 drops) was then added which immediately resulted in a pale salmon pink precipitate. The solid 3 was filtered washed with H2O (3 × 5.0 cm ) and left to air dry. The dried solid was recrystallised from a 1:1 acetone:H2O solvent mixture to give long pink/orange 2+ needles. Yield 0.239 g (90%) Mass spectrum: (HR-ESI) MeCN [ML3] m/z 2+ 263.0705 [100%] (calculated for [C30H24N6Ni1] , 263.0703).

3.3.3.5 cis-[Ru(phen)2Cl2]·2H2O

The synthesis of this complex follows a similar procedure to that of Sullivan et al.281

Commercially available RuCl3·xH2O (1.966 g, 7.27 mmol for x = 3.5), 1,10-phenanthroline (2.751 g, 15.3 mmol) and anhydrous lithium chloride, LiCl (2.053 g, 48.4 mmol) in DMF (13 cm3) were heated at reflux with stirring for 6 hours

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CHAPTER 3 during which time the reaction mixture changed colour from olive green to dark pink/purple. Once cooled to room temperature a black solid began to form. Acetone (65 cm3) was added and then the resultant mixture cooled in the freezer at -20°C 3 overnight. The black solid was filtered and washed with ice cold H2O (3 × 5 cm ) 3 followed by cold Et2O (3 × 5 cm ) then left to dry. Yield 2.768 g (67%). This complex was used as a synthetic precursor without further purification. 1H-NMR 3 3 (400 MHz; d6-DMSO; 300 K): δH 10.32 (d, JHH = 4.7 Hz, 2H), 8.69 (d, JHH = 8.2 3 3 3 Hz, 2H), 8.40 (d, JHH = 8.2 Hz, 2H), 8.33 (d, JHH = 8.2 Hz, 2H), 8.28 (d, JHH = 8.2 3 3 Hz, 2H), 8.21 (m, 2H), 7.77 (dd, JHH = 4.7 Hz, 2H), 7.32 (ddd, JHH = 8.2 Hz, 2H). This is a match to the spectrum reported in the literature.282

3.3.3.6 cis-[Ru(bipy)2Cl2]·2H2O

This complex was synthesised using the procedure as described in Section 3.3.3.5,281 replacing 1,10-phenanthroline with a molar equivalent of 2,2′-bipyridine. Yield 2.584 g (69%). This complex was used as a synthetic precursor without further 1 3 purification. H-NMR (400 MHz; d6-DMSO; 300 K): δH 9.95 (unresolved dd, JHH = 3 3 3 4.8 Hz, 2H), 8.63 (d, JHH = 8.2 Hz, 2H), 8.47 (d, JHH = 8.2 Hz, 2H), 8.06 (dt, JHH = 4 3 7.6 Hz, JHH = 1.2 Hz, 2H), 7.77 (unresolved dt, JHH = 7.6 Hz, 2H), 7.68 (unresolved 3 3 3 dt, JHH = 8.2 Hz, 2H), 7.51 (d, JHH = 5.3 Hz, 2H), 7.10 (unresolved td, JHH = 6.8 Hz, 2H). This is a match to spectra reported in the literature.282,283

3.3.3.7 [Ru(phen)3]Cl2·9H2O

This complex was prepared using a reported literature procedure.272 A solution of 1,10-phenanthroline (0.185 g, 1.03 mmol) in MeOH (20 cm3) was added to a solution of cis-[Ru(phen)2Cl2] ·2H2O (Section 3.3.3.5, 0.557 g, 0.98 mmol) in MeOH (100 cm3) and then heated at reflux for 1 hour with stirring, during which time the solution turned bright red. The reaction mixture was cooled to room temperature, filtered through a pad of Celite® and the solvent removed in vacuo. An aqueous solution of the crude mixture was then triturated with acetone (ca. 5 cm3) and the dark red solid was filtered and washed with cold acetone (2 × 2 cm3). The solid was recrystallised by vapour diffusion of acetone into H2O to give red thin prisms. Yield 0.574 g (67%). 2+ Mass spectrum: (HR-ESI) MeCN [ML3] m/z 321.0570 [100%] (calculated for

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2+ + [C36H24N6Ru1] , 321.0548), [ML3 + X] m/z 677.0787 [21%] (calculated for + [C36H24N6Ru1 + Cl] , 677.0789). Elemental Analysis Found: C, 49.46; H, 4.55; N, 1 9.68. Calculated for C36H42Cl2N6O9Ru1: C, 49.43; H, 4.84; N, 9.61. H-NMR 3 3 Spectrum: δH (400 MHz; D2O) 8.47 (d, JHH = 8.2 Hz, 6H), 8.12 (s, 6H), 8.00 (d, JHH 3 = 8.2 Hz, 6H), 7.49 (unresolved dd, JHH = 8.2 Hz, 6H). The spectrum is a match to that reported in the literature.284

3.3.3.8 [Ru(bipy)3]Cl2·7H2O

This complex was prepared using a reported literature procedure.272 A solution of 2,2′-bipyridine (0.166 g, 1.06 mmol) in MeOH (20 cm3) was added to a solution of 3 cis-[Ru(bipy)2Cl2] ·2H2O (Section 3.3.3.6, 0.526 g, 1.01 mmol) in MeOH (100 cm ) and heated at reflux for 1 hour with stirring, during which time the solution turned bright red. The reaction mixture was cooled to room temperature, filtered through a pad of Celite® and the solvent removed in vacuo. An aqueous solution of the crude mixture was then triturated with acetone (ca. 5 cm3) and the red solid filtered and washed with cold acetone (2 × 2 cm3). The solid was recrystallised by vapour diffusion of acetone into H2O to give red multifaceted prisms. Yield 0.550 g (71%). 2+ Mass spectrum: (HR-ESI) MeCN [ML3] m/z 285.0565 [100%] (calculated for 2+ + [C30H24N6Ru1] , 285.0548), [ML3 + X] m/z 605.0785 [15%] (calculated for + [C30H24N6Ru1 + Cl] , 605.0789). Elemental Analysis Found: C, 46.74; H, 4.61; N, 1 10.97. Calculated for C30H38Cl2N6O7Ru1: C, 47.00; H, 5.00; N, 10.96. H-NMR 3 3 Spectrum: δH (400 MHz; D2O) 8.44 (d, JHH = 8.2 Hz, 6H), 7.95 (dt, JHH = 8.2 Hz, 4 3 3 JHH = 1.8, 6H), 7.34 (unresolved dd, JHH = 4.7 Hz, 6H), 7.27 (dt, JHH = 6.8 Hz,

4 284 JHH = 1.2, 6H). The spectrum is a match to that reported in the literature.

III 3.3.4 Synthesis of K3[M (ox)3]·xH2O complexes

3.3.4.1 K3[Mn(ox)3]·xH2O

This complex was synthesised according to the literature procedure of Cartledge and

285 Ericks. Powdered potassium permanganate, KMnO4 (2.307 g, 14.60 mmol) was added in very small portions to a stirred solution of oxalic acid, H2C2O4·2H2O 3 (11.811 g, 93.74 mmol) in H2O (75 cm , ca. 70°C). To the resultant milky white

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suspension, potassium carbonate, K2CO3 (2.612 g, 18.90 mmol) was added and the reaction mixture wrapped in aluminium foil and placed in an ice salt water bath.

Further KMnO4 (0.604 g, 3.82 mmol) was then added with stirring to the ice cold light protected solution. The white solid was then quickly separated from the cherry red filtrate via vacuum filtration and discarded. Ice cold EtOH (40 cm3) was then added to the coloured solution until small amounts of a deep red/purple crystalline precipitate were evident. The mixture was left to stand in an ice bath to further crystallise for ca. 1 hour before filtering the deep purple prismatic crystals and washing first with ice cold EtOH (2 × 10 cm3), then with ice cold acetone (2 × 10 cm3). The crystalline product was stored in vacuo over silica gel and protected from light with aluminium foil. Decomposition began after ca. 4 days (light pink colour) and after ca. 1 week decomposition was complete, resulting in a snow white solid. Yield 4.581 g (57%) based on anhydrous formula.

3.3.4.2 K3[Cr(ox)3]·2.5H2O

This complex was synthesised according to the procedure of Bailer et al.286 Powdered potassium dichromate, K2Cr2O7 (1.920 g, 6.53 mmol) was added very slowly to a vigorously stirring solution of potassium oxalate, K2C2O4·H2O (2.313 g, 3 12.55 mmol) and oxalic acid, H2C2O4·2H2O (5.508 g, 43.69 mmol) in H2O (80 cm ).

After the addition of all of the K2Cr2O7, the solvent was removed in vacuo to near dryness at which point small blue/black crystals began to form. An aqueous solution of the crude mixture was then triturated with EtOH (ca. 5 cm3) and the green/blue solid filtered and washed with cold EtOH (2 × 2 cm3). The solid was recrystallised by vapour diffusion of EtOH into H2O to give large iridescent blue/black rectangular prisms. Yield 4.865 g (80%). Elemental Analysis Found: C, 15.07; H, 0.73.

Calculated for C6H5CrK3O14.5: C, 15.06; H, 1.05. –ve ion mass spectrum: (HR-ESI) - - MeCN [ML2] m/z 227.9186 [100%] (calculated for [C4O8Cr1] , 227.8998), 2- 2- X[M(L)3] m/z 177.4380 [44%] (calculated for [C6O12K1Cr1] , 177.4216), - - X2[M(L)3] m/z 393.8327 [29%] (calculated for [C6O12K2Cr1] , 393.8069).

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3.3.4.3 K3[Fe(ox)3]·2.5H2O

This compound was synthesised according to the procedure of Johnson and although not stated the reaction mixture was protected from light at all times.287 A solution of 3 K2C2O4·H2O (3.008 g, 16.33 mmol) in hot H2O (15 cm ) was added slowly to a 3 stirring solution of FeCl3·6H2O (1.236 g, 4.57 mmol) in hot H2O (15 cm , ca. 70°C) resulting in a lime green solution. The reaction was cooled slowly in the dark then placed in an ice bath for ca. 1 hour to induce crystallisation. The bright green solid was vacuum filtered, washed with cold EtOH (2 × 5 cm3) and then recrystallised by vapour diffusion of EtOH into H2O to give photosensitive green square bipyramidal and rectangular prismatic crystals. Yield 1.983 g (90%). Elemental Analysis Found:

C, 15.02; H, 0.75. Calculated for C6H5FeK3O14.5: C, 14.94; H, 1.05. –ve ion mass - - spectrum: (HR-ESI) MeCN [ML2] m/z 231.9133 [100%] (calculated for [C4O8Fe1] , - - 231.8943), X2[M(L)3] m/z 397.8266 [16%] (calculated for [C6O12K2Fe1] , 397.8014).

3.3.4.4 K3[Ru(ox)3]·xH2O Method 1

The synthesis of this complex via this method and method 2 (outlined in Section 3.3.4.5) followed the literature procedures of Beattie et al.288 Although not stated in the paper, it is known that the process was conducted in the dark. A solution of 3 potassium hydroxide, KOH (0.747 g, 13.31 mmol) in H2O (1 cm ) was added dropwise to a stirring solution of RuCl3·xH2O (1.046 g, 3.87 mmol for x = 3.5) in 3 H2O (20 cm ). After 15 mins the black Ru(OH)3·xH2O precipitate was isolated by 3 vacuum filtration and washed with H2O (8 × 200 cm ). The washings involved vigorous stirring of the aqueous suspension of Ru(OH)3·xH2O for ca. 20 mins followed by separation of the black tarry solid by vacuum filtration and testing of the - filtrate for the presence of Cl anions with an aqueous solution AgNO3 (1 M). This washing process required 7 hours. This hydroxide intermediate was then added to a 3 boiling aqueous solution of H2C2O4·2H2O (1.981 g, 15.71 mmol, 10 cm ) and heated at reflux for 20 minutes at which point the black solid had dissolved and formed an olive green solution. Powdered K2C2O4·H2O (1.082 g, 5.87 mmol) was added with stirring to the hot solution and the resultant mixture heated at reflux for a further 20 mins, then cooled to ca. 40°C and poured onto EtOH (225 cm3) resulting in an immediate yellow/green principate. This solid was then isolated via vacuum

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CHAPTER 3 filtration, washed with ice cold EtOH (3 × 20 cm3) and then recrystallised by vapour diffusion of EtOH into H2O to give olive green needles and a large amount of an amorphous black pasty solid. Within 3 days the light/air-protected olive green crystalline material decomposed to a black oil. Yield before recrystallisation 1.026 g (48%).

3.3.4.5 K3[Ru(ox)3]·xH2O Method 2

A solution of RuCl3·xH2O (1.010 g, 3.74 mmol for x = 3.5) and K2C2O4·H2O 3 (2.360 g, 12.80 mmol) in H2O (20 cm ) was heated at reflux with vigorous stirring for 7 hours, during which time the solution changed colour from black/brown to clear olive green. Hot EtOH (50 cm3, ca. 70°C) was then quickly added resulting in the immediate formation of a black solid, which was then filtered warm. The solid was 3 then redissolved in H2O (3 cm ) and the resulting solution triturated with EtOH (20 cm3). The precipitate was then isolated by vacuum filtration and the filtrate tested - with an aqueous solution of AgNO3 (1 M) for the presence of Cl anions. The solid was redissolved and reprecipitated once more, at which time the filtrate tested negative for Cl- anions. As described in the previous method, the solid was isolated via vacuum filtration, washed with ice cold EtOH (3 × 20 cm3) and then recrystallised by vapour diffusion of EtOH into H2O to give olive green needles and plates. Within 1 week the light/air-protected olive green crystalline material decomposed to a black oil. Yield 1.348 g (65%). –ve ion mass spectrum: (HR-ESI) ‾ - MeCN [ML2] m/z 277.8839 [100%] (calculated for [C4O8Ru1] , 277.8638), ‾ - X2[M(L)3] m/z 443.7961 [11%] (calculated for [C6O12K2Ru1] , 443.7709), 2- 2- X[M(L)3] m/z 202.4206 [9%] (calculated for [C6O12K1Ru1] , 202.4036).

3.3.4.6 K3[Rh(ox)3]·2H2O

The preparation of this complex followed the synthetic procedure of Coronado et

289 al. Freshly dried RhCl3 (1.008 g, 4.82 mmol after 1 hour in an oven at 110°C),

H2C2O4·2H2O (2.030 g, 16.11 mmol) and AgNO3 (2.049 g, 12.06 mmol) were 3 suspended in a 1:1 H2O:EtOH mixture (40 cm ) and heated to 85°C. After 3 hours a white precipitate (most likely AgCl) formed and was separated from the bright orange solution by hot gravity filtration. Solid K2C2O4·H2O (1.242 g, 6.74 mmol)

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CHAPTER 3 was then added to the filtrate and the resulting mixture heated for another 2 hours at 85°C. The solution was then left to cool slightly (ca. 40°C), filtered through Celite® and then poured over EtOH (250 cm3) immediately precipitating a pale yellow solid. This solid was then isolated via vacuum filtration, washed with ice cold EtOH (4 × 3 20 cm ) and then recrystallised by vapour diffusion of EtOH into H2O to give bright orange prismatic crystals. Yield 1.856 g (74%). Elemental Analysis Found: C, 13.84;

H, 0.70. Calculated for C6H4K3O14.Rh: C, 13.85; H, 0.77. –ve ion mass spectrum: 2- 2- (HR-ESI) MeCN X[M(L)3] m/z 202.9328 [8%] (calculated for [C6O12K1Rh1] , ‾ - 202.9041), X2[M(L)3] m/z 444.7969 [7%] (calculated for [C6O12K2Rh1] , 444.7719), ‾ - [ML2] m/z 278.8831 [1%] (calculated for [C4O8Rh1] , 278.8648).

3.3.5 Binary co-crystallisation experiments

The binary co-crystallisation experiments discussed within this thesis fit into three general categories. The first are experiments between cationic metal complexes II 2+ of the type [M (L)n] , and are described first. Then experiments between anionic III 3- [M (ox)3] metal complexes are described. Finally, experiments involving metal complex cations and metal complex anions are described.

II 2+ 3.3.5.1 Binary co-crystallisation experiments involving [M (terpyR)2] complexes

The general co-crystallisation protocol was the same for all cationic metal complexes, and is described as follows. The two complexes to be co-crystallised (totalling ca. 20-100 mg) were accurately weighed into two separate glass vials. The complexes were then dissolved in the appropriate solvent or solvent mixture before being combined by the dropwise addition of the solution of one complex to the other. The solutes in the resultant co-solution were then crystallised via the appropriate method (usually slow of evaporation of 1:1 MeCN:H2O) to yield single co-crystals, which contained both complexes (after ca. 2 days). The crystallised sample was then visually assessed under an optical microscope equipped with a polariser for evidence of co-crystallisation. Attributes that were noted were crystal habit(s), colour(s) and twinning or aggregation. If co-crystallisation was thought to have occurred (as evident from microscope observations), representative single crystals were then

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freshly harvested from the mother liquor for SEM-EDX analysis. Each crystal was analysed at several different locations to test for homogeneity, while comparison measurements from different crystals within any given batch supplied information on the uniformity (or lack thereof) of co-crystallisation. For selected samples, SEM-EDX analysis was conducted on powdered crystals to gain information regarding the presence of concentration gradients. Where necessary, SEM-EDX studies were also performed on the residue remaining as a result of evaporating the mother liquor. Powder XRD patterns of each batch of co-crystals were recorded to obtain phase information for the bulk sample in each batch. Furthermore, SCXRD data were collected for selected stable single co-crystals that diffracted well during the pre-experiment. Each batch combination was conducted in triplicate to test reproducibility. All samples that appeared to maintain structural integrity under the SEM high vacuum conditions were treated as per the protocol described. A complete list of binary co-crystallisation experiments is provided in Table 4.

II 2+ 2+ Table 4: Summary of [M (L)2] and [Ru(L)2] binary co-crystallisation experiments showing the metal complexes involved, their colour and their relative ratio in solution (L = terpy, terpyOH, terpyPh).

Complex A (colour) Complex B (red) A:B ratio in solution

[Fe(terpy)2](PF6)2 (purple) [Ru(terpy)2](PF6)2

[Co(terpy)2](PF6)2 (tan brown) [Ru(terpy)2](PF6)2

[Ni(terpy)2](PF6)2 (light brown) [Ru(terpy)2](PF6)2 0.50:0.50 [Cu(terpy)2](PF6)2 (blue/green) [Ru(terpy)2](PF6)2

[Fe(terpyPh)2](PF6)2·MeCN·H2O (purple) [Ru(terpy)2](PF6)2

[Ni(terpyPh)2](PF6)2·4MeCN (tan brown) [Ru(terpy)2](PF6)2

[Cu(terpyPh)2](PF6)2·4MeCN (blue/green) [Ru(terpy)2](PF6)2 0.20:0.80, 0.50:0.50 and 0.80:0.20 III [Co (terpyOH)(terpyO)](BF4)2·3.5H2O (brown) [Ru(terpy)2](BF4)2 0.50:0.50

[Fe(terpyOH)2](BF4)2·H2O (purple) [Ru(terpy)2](BF4)2

[Ni(terpyOH)2](BF4)2·H2O (light brown) [Ru(terpy)2](BF4)2 0.50:0.50 and 0.05:0.95

[Cu(terpyOH)2](BF4)2·H2O (blue/green) [Ru(terpy)2](BF4)2

II 2+ 94 Based on previously known crystal packing features of some [M (L)2] complexes, additional co-crystallisation experiments were conducted, which were thought could produce interesting crystal structures. These are listed in Table 5.

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2+ 2+ Table 5: Summary of [Ni(L)3] and [Ru(L′)2] binary co-crystallisation experiments showing the metal complexes involved, their colour and their relative ratio in solution (L = phen, bipy, L′ = terpy, terpyPh).

Complex A Complex B A:B ratio in solution (pink) (red)

[Ni(phen)3](PF6)2·H2O [Ru(terpy)2](PF6)2

[Ni(bipy)3](PF6)2 [Ru(terpy)2](PF6)2 0.80:0.20 [Ni(phen)3](PF6)2·H2O [Ru(terpyPh)2](PF6)2·4MeCN

[Ni(bipy)3](PF6)2 [Ru(terpyPh)2](PF6)2·4MeCN

III 3.3.5.2 Binary co-crystallisation experiments involving K3[M (ox)3] complexes.

Several co-crystallisation experiments were conducted using a modified version of the general protocol described in Section 3.3.5.1. Crystallisations were conducted 3 using the vapour diffusion method of EtOH into H2O (1 cm of H2O for 20 mg of total solid). Freshly synthesised K3[Fe(ox)3]·2.5H2O and K3[Ru(ox)3]·xH2O (x is ca. 4.5288) was used. Figure 19 shows a schematic of the vapour diffusion apparatus used for the co-crystallisation experiments. All co-crystallisations, regardless of the stability of the complexes, were conducted in the dark and were left undisturbed for ca. 3 days.

Lid and Parafilm

Vial 2: EtOH Vial 1: Solid material of A 3 days Vial 1: and B in EtOH/H2O A and B (total ca. 20 mg) dissolved in H2O 3 (1 cm ) Vial 2: EtOH Figure 19: Schematic describing co-crystallisation experiments of complexes A and B via vapour diffusion of ethanol into water.

Due to the fragility of these materials under vacuum, characterisation via SEM-EDX was problematic. It was noted that the crystals appeared cracked and weathered immediately after carbon-coating and further deteriorated after about 30 minutes under the vacuum of the SEM. Once re-exposed to atmospheric conditions, the crystals completely deteriorated into a powder. Raman microscopy was instead

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CHAPTER 3 employed as the primary characterisation technique for quantitative analysis using the position of the carbonyl stretching frequency. Each single co-crystal was prepared and characterised individually before the next was harvested from solution.

Once viewed under an optical microscope, selected crystals were removed from the mother liquor and placed on the stage of the Raman microscope. Although under low magnification the single crystals appeared to be well formed with lustrous faces and sharp edges, it was evident under higher magnification that the faces possessed several defects. Therefore, after viewing each face under the Raman microscope, crystals were oriented so that the smoothest face was analysed. It was discovered that these defects acted as fault lines once the crystals were out of the mother liquor (ca. 24 hours) and so it was important that the measurements be completed in the shortest amount of time. The selected face was then photographed using the WiRE Raman Renishaw software and then analysed at 3-4 different positions using optimised measurement conditions and noting the location of each measurement.* The photograph was then used to trace out regions for line and two-dimensional mapping.† A select few samples were subjected to Confocal Raman microscopy depth-profile mapping.‡ This variation on the usual Raman technique required ca. 15-20 hours and was conducted following line and area maps.

Once the Raman measurements were completed the crystal was then carefully mounted to have the same surface facing up and then prepared for SEM-EDX as described earlier. Where possible, EDX measurements were taken from the same locations as the Raman measurements for the purpose of validating the quantitative use of the carbonyl stretching band in the Raman spectrum. EDX analysis was limited to 30 minutes per crystal. A full discussion regarding the use of Raman microscopy for quantitative analysis can be found in Section 5.2.1. A summary of co-crystallisation experiments showing all metal complexes involved, their relative

*Spectra were recorded using a 50× long working distance objective with a 785 nm laser at 10% power (as any greater power damaged the sample) co-adding triplicate 20 second measurements. Full spectra were measured using the extended method while spectra between 1300-1800 cm-1 were taken using the static method. †Line and area maps were obtained from a series of static scans with an exposure time of 10 seconds (usually 5-10 µm apart for line maps and square areas of 20 × 20 µm to 50 × 50 µm for area maps) using the same objective and laser power. ‡ Confocal Raman spectra were recorded at 100% laser power starting from depths of up to 500 µm. Spectra were taken at 50 µm intervals using the static method with exposure times 45-60 minutes.

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CHAPTER 3 solution concentration and whether or not single crystals resulted is provided in Table 6. The notes at the foot of the table outline the nature of the instability of the pure complexes.

III 3- III 3- Table 6: Summary of [M (ox)3] and [M (ox)3] co-crystallisation experiments showing all metal complexes involved and their relative solution concentrations. The notes at the foot of the table outline the nature of the instability of the pure complexes.

Complex A Complex B A:B ratio in solution * K3[Cr(ox)3]·2.5H2O K3[Mn(ox)3]·xH2O 0.50:0.50 0.10:0.90, 0.30:0.70, 0.50:0.50, † K3[Cr(ox)3]·2.5H2O K3[Fe(ox)3]·2.5H2O 0.70:0.30 and 0.90:0.10 0.10:0.90, 0.30:0.70, 0.50:0.50, ‡ K3[Cr(ox)3]·2.5H2O K3[Ru(ox)3]·xH2O 0.70:0.30 and 0.90:0.10

K3[Cr(ox)3]·2.5H2O K3[Rh(ox)3]·2H2O 0.50:0.50 * † K3[Mn(ox)3]·xH2O K3[Fe(ox)3]·2.5H2O 0.50:0.50 * ‡ K3[Mn(ox)3]·xH2O K3[Ru(ox)3]·xH2O 0.50:0.50

† ‡ 0.10:0.90, 0.30:0.70, 0.50:0.50, K3[Fe(ox)3]·2.5H2O K3[Ru(ox)3]·xH2O 0.70:0.30 and 0.90:0.10

K3[Fe(ox)3]·2.5H2O K3[Rh(ox)3]·2H2O 0.50 *Solid and solution highly photosensitive and thermosensitive. † Highly photosensitive solution state, moderately photosensitive solid state. ‡Solid and solution highly photosensitive and air sensitive.

3.3.6 K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O epitaxial experiments

III III In order to better understand the results obtained from the K3[M (ox)3]·2.5H2O (M = Fe, Cr) co-crystallisation experiments, several epitaxial experiments were attempted. In general terms, epitaxial experiments involve immersing a crystal (seed) into a solution containing a desired compound so that more crystalline material can deposit onto the seed substrate. Epitaxial crystals were formed by immersing III III * K3[M (ox)3]·2.5H2O seed crystals (M = Cr and/or Fe) into saturated solutions of III III K3[M (ox)3](aq/EtOH) (M = Cr or Fe or an equimolar mixture of both). Immersion of seed crystals was achieved by either directly placing the crystals in the vial containing the saturated solution (ca. 5-10 seeds) or by first adhering the seed crystals to a glass fibre with cyanoacrylate adhesive and then suspending it in solution (1 or 2 seeds). It is important to note that only saturated solutions were used in order to limit partial dissolution of the seed crystals. Table 7 summarises the seeds

* Freshly synthesised K3[Fe(ox)3]·2.5H2O was used. 67

CHAPTER 3 and solutions used in the epitaxial studies. Each epitaxial experiment was repeated at least once to ensure reproducibility giving a total of at least 16 experiments. Epitaxial growth crystals were viewed under an optical microscope before characterisation by Raman spectroscopy.

Table 7: Summary of the composition of the seed crystals and the saturated solutions used to crystallise epitaxial growth crystals.

* † Seed crystal(s) Sat. solution(aq/EtOH)

K3[Fe(ox)3]·2.5H2O K3[Cr(ox)3]

K3[Cr(ox)3]·2.5H2O K3[Fe(ox)3]

K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O K3[Cr(ox)3]

K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O K3[Fe(ox)3]

K3[Fe(ox)3]·2.5H2O 1:1 mixture of K3[Cr(ox)3] and K3[Fe(ox)3] * Seed crystals were grown as per the vapour diffusion recrystallisation method (EtOH into H2O). †Saturated solutions were prepared by first dissolving the appropriate metal complex (or a 1:1 mixture of both) in H2O and then quickly adding EtOH until the first sign of precipitation was observed. The solution was then filtered through a nylon filter fitted to a syringe. Saturated solutions were used immediately and any excess discarded.

II III 3.3.7 Synthesis of [M (L)3][NaM (ox)3] co-ordination metal-organic frameworks

The synthesis of these frameworks followed the procedure of Decurtins et al.290 An II 2+ II aqueous solution of [M (L)3] (0.01 M; M = Ni and/or Ru; L = 2,2′-bipyridine and/or 1,10-phenanthroline) was added to a stoichiometric quantity of an aqueous III 3- III * solution of [M (ox)3] (0.01 M; M = Cr and/or Fe ) with stirring at room temperature. An excess amount of aqueous NaCl (0.02 M) was then added and contrary to the literature descriptions, no immediate precipitate was observed. All 0.01 M solutions were freshly prepared by dissolving a known amount of each respective metal complex in a class A volumetric flask (5 or 10 cm3), making up to the mark and then dispensed using an automatic micropipette into glass vials. All experiments were repeated at least three times, were conducted in the dark and allowed to crystallise in complete darkness for ca. 14 days.

* Freshly synthesised K3[Fe(ox)3]·2.5H2O was used. 68

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To avoid any possibility of ligand exchange, combinations with both

K3[Fe(ox)3]·2.5H2O and [Ni(L)3]Cl2·xH2O were avoided due to the labile nature of the metals. Samples were analysed by SEM-EDX; however, only samples that retained crystallinity were analysed using XRD techniques. A summary of the co- crystallisation experiments showing all of the metal complexes involved and the formula (where known) of the resulting co-crystalline co-ordination framework is provided in Table 8.

II 2+ III 3- Table 8: Summary of co-crystallisation experiments between [M (L)3] and [M (ox)3] showing all metal complexes involved and their relative ratios in solution. Aqueous NaCl (0.02 M) was added to each experiment.

Complexes involved in dilution (xsolution = 0.50) Counterion Complex

Complex A* Complex B* Complex C* A:B:C ratio in solution

II 2+ III 3- Homoleptic dilutions: Co-crystallisation of [M (bipy)3] with [M (ox)3]

[Ni(bipy)3]Cl2 [Ru(bipy)3]Cl2 K3[Cr(ox)3] 0.50:0.50:1

K3[Cr(ox)3] K3[Fe(ox)3] [Ru(bipy)3]Cl2 0.50:0.50:1

II 2+ III 3- Homoleptic dilutions: Co-crystallisation of [M (phen)3] with [M (ox)3]

[Ni(phen)3]Cl2 [Ru(phen)3]Cl2 K3[Cr(ox)3] 0.50:0.50:1

K3[Cr(ox)3] K3[Fe(ox)3] [Ru(phen)3]Cl2 0.50:0.50:1

II 2+ III 3- Different ligand dilutions: Co-crystallisation of [M (L)3] (L = bipy, phen) with [M (ox)3]

[Ni(bipy)3]Cl2 [Ru(phen)3]Cl2 K3[Cr(ox)3] 0.50:0.50:1

[Ni(phen)3]Cl2 [Ru(bipy)3]Cl2 K3[Cr(ox)3] 0.50:0.50:1 *Metal complex hydrates were used. The hydration of each complex is not shown but was accounted for when preparing the solutions.

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CHAPTER 4: Co-crystallisation systems incorporating II 2+ [M (terpyR)2] complexes

II 4.1 Background: The [M (terpyR)2]X2 metal complexes and the terpy motif

The compound 2,2′:6′,2′′-terpyridine (terpy), for which the chemical structure and numbering system are shown in Figure 20, was first synthesised by Morgan and Burstall in 1932, by the oxidative coupling of pyridine using anhydrous ferric chloride.291 This group was also the first to report the coordination of a metal to terpy by synthesising a variety of mononuclear and trinuclear platinum complexes, with various mono-anionic species included in the coordination sphere and/or acting as counter ions.292 Five years later Morgan and Burstall (1937) reported the first II II syntheses of bis-terpy complexes with the formula [M (terpy)2]X2 (M = Cr, Fe, Co, Ni, Ru, Os; X = Cl-, Br-).293 The introduction, results and discussion presented in this II II chapter refer to complexes of the formula [M (terpyR)2]X2, where M is a first or second row transition metal, terpyR is either the unsubstituted terpy (R = H) or the 4′-functionalised terpyOH or terpyPh ligand and X = small mono-anionic counterion.

4' 3' 5' c 3 R 3'' 4 4'' o N o R 1' R 5 N1 1''N 5'' 6 6'' Figure 20: The structure of 2,2′:6′,2′′-terpyridine (terpy) showing the atom numbering of each pyridyl ring. The two outer rings are denoted Ro while the central pyridyl ring is labelled Rc. Note the 4′-carbon position, which may be substituted and written in formulae as (terpyR; R = OH, Ph).

II 2+ The following discussion aims to outline the key features of [M (terpyR)2] II 2+ complexes and the terpy motif. Many of the [M (terpyR)2] complexes used during this research exhibit the same features and interact through the same supramolecular chemical interactions as those introduced here.

Terpy most commonly behaves as a meridional-N3-tridentate chelating ligand, coordinating to the metal. Thus, for di-cationic transition metals that form octahedral complexes, two terpy ligands complete the coordination sphere to make

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II 2+ [M (terpy)2] species. Typical N-M-N′ bond angles for these types of complexes are less than 90° and as such, they often display a distorted octahedral geometry.* 294-303 II 2+ The dimensions of [M (terpy)2] units vary depending on the nature of the coordinating metal.† Figure 21 shows the orthogonal arrangement of the two terpy II 2+ ligands in [M (terpy)2] complexes as viewed perpendicular to and along the S4 axis.

S4 axis

II 2+ Figure 21: The orthogonal arrangement of the terpy ligands of typical [M (terpy)2] cations as viewed perpendicular to the S4 axis (left) and along the S4 axis (right). Carbon atoms are represented in green, hydrogen atoms in white, nitrogen atoms in blue and the metal ion in red.

II 2+ As a consequence of this orthogonal arrangement, [M (terpy)2] complexes are able to engage in a parallel 4-fold aryl embrace (P4AE) consisting of one OFF and two EF interactions per complex pair in the solid state (Figure 22). This specific set of interactions, which is now known as the terpy embrace or primary terpy motif, was first observed by Figgis et al. in 1983 as a common crystal packing arrangement

2+ 294 adopted by [Co(terpy)2] complexes.

* The N-M-N′ bond angles (measured from reported crystal structures) appear to be consistent for 2+ each different metal ion (within 2°) except for [Co(terpy)2] complexes, which have N-M-N′ angles ranging from 76-84°. † II 2+ A more in-depth explanation regarding the dimensions of [M (terpy)2] complexes can be found in the results section of this chapter (Section 4.3.1).

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Shallow groove

Deep groove

II 2+ Figure 22: The terpy embrace motif between a pair of [M (terpy)2] complexes. The ligands involved in the OFF interaction lie in parallel planes (outlined in red box and red double-headed arrow), while EF interactions involve ligands perpendicular to each other (yellow single-headed arrows). The EF interactions occur orthogonally to the OFF interactions. For each type of interaction it is only the Ro pyridyl rings involved. The Rc rings, although not involved in either interaction, create the walls of voids giving rise to deep and shallow grooves that are capable of accommodating solvates and counterions. Deep grooves are framed by parallel faces of Rc rings (blue shaded area), while shallow grooves are bordered by the hydrogen atoms of Rc and Ro rings (pink shaded area).

More recently, in-depth crystal packing analysis has revealed the terpy motif to be II 2+ II 2+ II 2+ prevalent among, [M (terpy)2] , [M (terpyOH)2] and many [M (terpy-like)2] complexes.*32,34,94,121,271,294 These interactions arrange the complexes in a two-dimensional grid-like array called the two-dimensional (2D) terpy embrace. This grid structure is shown in Figure 23 and Figure 24.

II 2+ Figure 23: Ball and stick representation showing the interactions between four [M (terpy)2] complexes leading to the “infinite” grid-like structure called the two-dimensional (2D) terpy embrace. As with previous figures, OFF interactions are represented by the double-headed red arrows, while single-headed yellow arrows represent EF interactions. This motif propagates in all four directions, as indicated by the solid black arrows. Hydrogen atoms have been omitted for visual clarity.

* II 2+ [M (terpy-like)2] complexes are complexes that have similar structures and geometries to the II 2+ archetypal [M (terpy)2] complexes. These “terpy-like” compounds are typically meridional-N3-tridentate ligands with terminal five or six membered N-heterocycle groups. 72

CHAPTER 4

Shallow grooves

Rc cavity

Deep grooves

Figure 24: Space-filled representation of an expanded 2D terpy embrace layer containing nine II 2+ [M (terpy)2] complexes as viewed from the top (left), side (centre) and bottom (right). The black dotted squares (shown in the top and bottom views) highlight the four complexes represented in Figure 23. Deep grooves are not fully boxed in by complex pairs but instead are segmented into staggered cavities (Rc cavities shown by the transparent white boxes in the diagram on the far left). The l × w × d of these cavities are ca. 7.0 × 5.0 × 4.5 Å and link together to form a linear groove (thick blue rectangle) that runs the length of the 2D grid. Shallow grooves (thin pink rectangle) are also continuous and run perpendicular to deep grooves on the same surface. On the opposite side, like grooves are perpendicular to each other as evident by comparing top and bottom views.

The 2D layers of complexes exhibiting the 2D terpy embrace stack to form three-dimensional (3D) structures. The displacement of adjacent 2D layers in a II direction parallel to the lattice plane is a distinctive trait shared by all [M (terpy)2]X2 II - and [M (terpyOH)2]X2 structures, where X is a small monoanion such as BF4 . This stacking arrangement allows a portion of the Rc pyridyl ring of complexes in one layer to protrude slightly into the grooves of a neighbouring layer. Thus, the groove (deep or shallow), which is partially occupied, depends on one of three stacking variations of the layers.*32,271 Analyses of literature crystal structures revealed that deep grooves were also able to completely house relatively small counterions, such - - - - as NO3 , ClO4 , BF4 , PF6 and sometimes include small solvent molecules, such as II water. These anion and solvent molecules in [M (terpyOH)2]X2 structures form hydrogen bonds with the hydroxyl group of the terpyOH ligand. These interlayer II hydrogen bond arrangements are not present for [M (terpy)2]X2 as there are no hydroxyl groups on the unsubstituted terpy ligand. Despite this difference, the same II interlayer distances were found for [M (terpyOH)2]X2 as those found for II [M (terpy)2]X2 (ca. 10Å) indicating that the 4′-functionalisation of the terpy ligand with an OH group had little steric effect on the stacking of the 2D layers.271

* The three main stacking variations are; 1) parallel, where the planes of the ligands in adjacent layers are parallel to each other and are related by inversion or reflection symmetry; 2) angled, where the ligand planes in complexes of neighbouring layers stack at ca. 45° to one another and are related by 21 screw symmetry 3) perpendicular, where the planes of the ligands in contiguous layers are at 90° to one another.

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II 2+ The supramolecular chemistry present in [M (terpyPh)2] systems is more varied II 2+ II 2+ than that in either [M (terpy)2] and [M (terpyOH)2] systems. Nevertheless, II 2+ [M (terpyPh)2] complex pairs interact through the same terpy embrace that is II 2+ II 2+ observed between pairs of [M (terpy)2] and [M (terpyOH)2] complexes. II 2+ Structures of [M (terpyPh)2] , are known to exhibit less robust analogues of the 2D terpy embrace with interlayer separations as large as ca. 16 Å. These structures are often highly solvated with volatile solvent molecules such as MeCN, which act as space occupiers and lattice supports. Consequently, evaporation of these molecules causes the lattice to collapse. Given that the grooves of one layer accommodate counter-ions, solvate species and portions of metal complexes from adjacent layers, it is not surprising that large substituents on the 4′-carbon atom of the Rc ring (such as a phenyl group) disrupt the terpy motif.32-34,94,121,266,271,304,305

II 2+ Although the 2D terpy embrace motif is prevalent among most [M (terpy)2] and II 2+ [M (terpyOH)2] systems, the various structures that form belong to a multitude of space groups ranging from low symmetry triclinic P1¯ to high symmetry P4¯21c tetragonal space groups. The differences in symmetry present for the various structures are usually due to the size and complexity of counterions and the nature of II 2+ the crystallising solution. Table 9 summarises the various [M (terpy)2] and II 2+ - [M (terpyOH)2] crystal structures that have small counterions such as PF6 , which are available in the CSD (in chronological order of publication).51 For many of the structures in Table 9, the positions of counterions and solvate species were found to be rotationally disordered.

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II 2+ Table 9: Summary of crystal structures (in chronological order of publication) of [M (terpy)2] , and II 2+ [M (terpyOH)2] complexes.

CSD REFCODE Year Compound Formula Space Group

TERPYC01 1971 [Cu(terpy)2](NO3)2 I41/a

TPYCOB 1974 [Co(terpy)2]Br2·3H2O P1¯

TERPCO 1976 [Co(terpy)2](SCN)2·2H2O P1¯

BEJPUB 1982 [Cu(terpy)2](PF6)2 P4¯21c

BIKJUA 1982 [Ni(terpy)2](PF6)2 P212121

BIYJOI 1982 [Co(terpy)2](ClO4)2·0.5H2O I41/a

CAPSAN 1983 [Co(terpy)2](ClO4)2·H2O I41/a * CASXID 1983 [Co(terpy)2]I2·2H2O P42/n

DANMOU 1985 [Fe(terpy)2](ClO4)2·H2O P21

FADJAW 1986 [Co(terpy)2](NO3)2·2H2O I41/a

SIBWEF 1990 [Cu(terpy)2]Br2·3H2O P1¯

ZARNIP 1995 [Ni(terpy)2](ClO4)2·H2O P21 † GOGDIP 1998 [Ru(terpy)2](ClO4)2·H2O I41/a

GOGDOV 1998 [Os(terpy)2](ClO4)2·0.5H2O P21/n

LOCREA 1999 [Ru(terpy)2](PF6)2·Me2CO P21/c

SUVGAR 1999 [Ru(terpy)2](PF6)2·MeCN P41

BIYJOI01 2001 [Co(terpy)2](ClO4)2·0.5H2O P42/n

NELKEU 2001 [Cu(terpy)2](ClO4)2·H2O I41/a

XENWAO 2001 [Mn(terpy)2](ClO4)2·0.5H2O P43

XENWES 2001 [Fe(terpy)2](ClO4)2·0.5H2O P21

WOWZEN 2001 [Co(terpyOH)2]I2·H2O P21

BINZAA 2004 [Mn(terpy)2](NO3)2·2H2O I41/a

XAHLIC 2004 [Mn(terpy)2]I2·3H2O P21/n

CAPXUN 2005 [Fe(terpyOH)2](BF4)2·H2O P1¯

CAPYEY 2005 [Ru(terpyOH)2](BF4)2·H2O P1¯

CAPYIC 2005 [Cu(terpyOH)2](BF4)2·H2O P21

CAPYOI 2005 [Ni(terpyOH)2](BF4)2 P212121

CAZJUJ 2005 [Ru(terpy)2]Cl2·6H2O P21/c

NAVGEX 2005 [Ni(terpyOH)2](N(CN)2)2·H2O P1¯

XAJVOU 2005 [Ni(terpy)2](PF6)2·DMF P21/n

XAJVUA 2005 [Ni(terpy)2](PF6)2·Me2CO P212121

XAMMUU 2005 [Ni(terpy)2](NO3)2·0.5H2O I41/a

PEJHOC 2006 [Co(terpyOH)2](BF4)2·H2O P21

PEJHOC01 2006 [Co(terpyOH)2](BF4)2·H2O P1¯

PEJJIY 2006 [Co(terpyOH)2]I2·H2O P21/c

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PEJJOE 2006 [Co(terpyO)(terpyOH)](PF6)2 P21/c

LIDTUO 2007 [Zn(terpy)2](NO3)2·2H2O P42/n § MIWQAL 2008 [Mn(terpyOH)2](ClO4)2 P21/n

GUHPIJ 2009 [Ru(terpy)2]Cl2·DCM P21/c

QUNZAB 2009 [Ru(terpy)2](BF4)2 Cc n FAGGOL 2010 [Ni(terpy)2]SO4· PrOH I4¯

FAGHAY 2010 [Ni(terpyOH)2]SO4·EtOH·MeOH·0.5H2O P1¯ ‡ WALVEM 2010 [Co(terpy)2](BF4)2 Cc

XAHFAP 2010 [Co(terpy)2](PF6)2·MeCN P43

OMUTUM 2011 [Cd(terpy)2](NO3)2·2H2O I41/a

BARRAP 2012 [Ni(terpy)2](PF6)2·MeCN P41 *Measured at 120 and 295 K. †No coordinates available. ‡Measured at 30, 100, 150, 200, 250, 300, 325, 350 and 375 K. §Measured at 100 and 150K

A 4.2 Background: Previous research into the co-crystallisation of [M (L)n]X2 B A B with [M (L)n]X2 to form [M xM 1-x(L)n]X2 co-crystals.

As introduced in Section 1.6.3, members of the McMurtrie group have over the past few years focused on the use of supramolecular motifs to form single co-crystals of a predictable structure containing two or more different metal complexes. Single A B co-crystals of the general formula [M xM 1-x(L)n]X2 were prepared from solutions A B A B containing various relative ratios of [M (L)n]X2 to [M (L)n]X2 (M , M = different first or second row transition metals, L = polypyridyl ligands such as - 1,10-phenanthroline and X = monoanion such PF6 ). In addition to the binary A B A B homoleptic systems of [M xM 1-x(phen)3](PF6)2 and [M xM 1-x(bipy)3](PF6)2 that were mentioned in Section 1.6.3, experiments also included heteroleptic systems A B such as [M (phen)3]x[M (phen)2(bipy)]1-x(PF6)2 and A B [M (bipy)3]x[M (phen)2(bipy)]1-x(PF6)2 and different ligand combinations, such as A B * [M (bipy)3]x[M (phen)3]1-x(PF6)2. Results from these systems demonstrated that through the exploitation of known crystalline supramolecular motifs, it was possible to form co-crystals that contained different metal complexes.261,306,307

* Homoleptic co-crystallisation experiments refer to systems in which all metal complexes have identical ligands and therefore complexes only differ in the metal centre. Heteroleptic systems involve metal complexes that have more than one type of ligand coordinated to the metal. The term different ligand is used throughout this thesis to describe experiments involving different homoleptic complexes co-crystallised together, i.e. the ligands of one complex are different to the ligands of the other complex species.

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It was therefore hypothesised that systems with a dominant supramolecular motif, such as those exhibiting the 2D terpy embrace, would be the most suitable for co-crystallisation experiments due to the predictability afforded by co-crystallising complexes capable of similar intermolecular interactions. Furthermore, robust motifs such as the 2D terpy embrace are hypothesised to better tolerate the changes to the crystal structure resulting from the incorporation of different metal complexes due to the intermolecular interactions present between metal complex pairs.

Preliminary binary co-crystallisation experiments involving first row transition metal A B systems bearing terpyridyl ligands of the type [M xM 1-x(terpy)2]X2 and A B II - - - [M xM 1-x(terpyOH)2]X2 (M = Fe, Co, Ni, Cu; X = PF6 , BF4 , I ) were previously conducted and the resulting co-crystals analysed by SEM-EDX.306 An example of the data from one co-crystallisation series is shown in Figure 25. This figure plots the SEM-EDX data measured from co-crystals of the general formula

[NixCu1-x(terpy)2](PF6)2, which were formed from solutions containing various ratios of [Ni(terpy)2](PF6)2 relative to [Cu(terpy)2](PF6)2. The ratios of the metal complexes in the co-crystallising solutions (batches) are shown on the x axis (xsolution = 0.10 to 0.90 in 0.10 increments), while the concentrations of metal complexes in the co-crystals as determined by SEM-EDX are shown on the y axis (xsolid). The xsolution and xsolid values pertain to the [Ni(terpy)2](PF6)2 concentration in the solution and solid states respectively. The equation of the trend line, the standard errors for the slope, y intercept and R2 correlation coefficient are also shown.

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SEM-EDX:EDX GRAPHICAL Nix (solution) vs. SUMMARY: Nix (solid) [Niforx Cu[Ni1x-xCu(terpy)1-x (terpy)2](PF6)2](PFco-crystals6)2 system 1.00

0.90

0.80

0.70

0.60

solid solid x

x 0.50 solid

x y = 0.988 ± 0.010x + 0.013 ± 0.006

Ni Ni Ni R2 = 0.994 0.40

0.30

0.20

0.10

0.00 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 x solution Ni xsolution Figure 25: Plot of EDX results from previous experiments conducted by members of the McMurtrie group of [NixCu1-x(terpy)2](PF6)2 where xsolution = 0.10 to 0.90 in 0.10 increments. For each batch of experiments nine data points were collected (xsolid) but a record was not kept of which points originated from which crystal. The equation of the trend line together with the standard errors for the slope and y intercept are also shown.

The data points enclosed in the red box in Figure 25 above were measured from co-crystals grown from a solution containing 10% [Ni(terpy)2](PF6)2, while the data points enclosed in the green box originated from co-crystals grown from a solution containing 40% [Ni(terpy)2](PF6)2. The points in the red box heavily overlap one another and all contain ca. 10% [Ni(terpy)2](PF6)2 in the solid state. Conversely, the points in the green box only slightly overlap and are scattered above and below the trend line with xsolid values of ranging from 0.37 to 0.45 i.e. these co-crystals, which were grown from a solution containing 40% [Ni(terpy)2](PF6)2 contain between 37% and 45% [Ni(terpy)2](PF6)2 in the solid state. This observation was more pronounced at xsolution values between 0.40 and 0.60. These results and those obtained from other systems indicated that single crystals grown from any particular co-crystallisation batch may range in composition i.e. xsolid single crystal 1 ≠ xsolid single crystal 2. It is important to note that all single co-crystals analysed were found to have some proportion of both metal complexes.

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The points outlined by the blue box are also noteworthy. These measurements all lie above 0.60. This result alone signified the possibility of a solubility bias between complex species but in the presence of the other measurements it strongly indicates that the sample size for this batch was too small. In fact, it likely that the sample sizes from all of the batches for the system shown in Figure 25 and others were insufficient especially given the range for the 0.50:0.50 batch was smaller than the range of values for the batches shown either side of it.

It is important to note that all the data points in Figure 25 are represented by blue markers because it was not noted which measurement originated from which co-crystal. This was a major shortcoming of these preliminary experiments as results generally suggested that xsolid ≠ xsolution yet it was unclear if the measurements within a batch were from different regions on a single co-crystal or from different single co-crystals. Furthermore, although several co-crystallisation experiments were conducted, only some of the co-crystals were analysed by SEM-EDX, and none were characterised by powder or single crystal XRD. Therefore, no information relating to phase or structure was collected. Lastly, it is important to note that SEM-EDX is a surface technique, analysing to depths of ca. 5 µm, and since crystals grow in three dimensions it would be possible for measurements taken from the surface to differ from measurements taken from the core. Differences between surface and core measurements would imply the formation of co-crystals with concentration gradients.

Therefore, experiments conducted within this work aimed to address these issues and answer the questions raised from those preliminary experiments in order to better understand the mechanism(s) driving co-crystal growth. Further research into the A B composition, phase and crystal structure of [M xM 1-x(terpyR)2]X2 single co-crystals was the focus of the work presented here.

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4.3 Results and discussion

II 2+ During this research several co-crystallisation experiments involving [M (terpyR)2] complexes were conducted. Section 4.3.1 presents results obtained from homoleptic II experiments where [M (terpy)2](PF6)2 complexes were co-crystallised with

[Ru(terpy)2](PF6)2, to form co-crystals of the general formula II II [M xRu1-x(terpy)2](PF6)2 (M = Fe, Co, Ni, Cu). Section 4.3.2 discusses the results II obtained from different ligand experiments where [M (terpyOH)2](BF4)2 or III [Co (terpyO)(terpyOH)](BF4)2 complexes were co-crystallised with

[Ru(terpy)2](BF4)2, to form co-crystals of the general formula II II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (M = Fe, Co, Ni, Cu). The results from II different ligand co-crystallisation experiments where [M (terpyPh)2](PF6)2 II complexes (M = Fe, Ni, Cu) were co-crystallised with [Ru(terpy)2](PF6)2 and where

[Ru(terpyR)2](PF6)2 (terpyR = terpy, terpyPh) were co-crystallised with either

[Ni(phen)2](PF6)2 or [Ni(bipy)2](PF6)2 are discussed in Section 4.3.3.

Results obtained from previous work indicated that single crystals of the type A B A [M xM 1-x(L)n]X2 grown from solutions where the relative ratio between [M (L)n]X2 B and [M (L)n]X2 was between 0.40-0.60 (xsolution) displayed the largest range in xsolid values. It was due to this repeated observation that experiments conducted during this research focused on combinations where xsolution = 0.50. Although ligand exchange is not a concern for homoleptic combinations, it is a major issue for different ligand systems, so a kinetically inert ruthenium complex was used as one of the complex species in each co-crystallisation experiment.59,60

Throughout this project, SEM-EDX has been used as a quantitative characterisation technique for elemental analysis of single co-crystals. Co-crystals to be analysed were harvested with a pipette directly from the glass vial in which they were grown, and deposited onto carbon tape that was adhered to an aluminium SEM stub. The small amount of mother liquor that was also transferred by the pipette was removed using a Kimwipe® to prevent a thin film of residue forming on the crystals. The crystals were then carbon-coated before being analysed. For each co-crystallisation batch, at least ten intact single co-crystals were analysed, each in at least three

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CHAPTER 4 different areas.*Experiments were conducted in triplicate to make certain the technique was reliable and the results were reproducible. Since SEM-EDX is a surface technique, a selection of co-crystals were carefully crushed and re-analysed. Results obtained from crushed crystals were compared with surface measurements. The complete SEM-EDX protocol developed for this project, which outlines all the details of sample preparation, selection and measurement can be found in the preparative experimental details chapter in Sections 3.2.1 and 3.3.5.1. In addition, a brief discussion outlining the technical aspects of the SEM-EDX technique and its use throughout this research as a means of elemental analysis can be found in Appendix A.

Where possible, co-crystals were also characterised using powder and single crystal X-Ray diffraction techniques. Powder XRD patterns, single crystal diffraction (SCXRD) and refinement data are discussed in the relevant sections.

II 4.3.1 [M xRu1-x(terpy)2](PF6)2 co-crystallisation systems

II II Several co-crystals with the general formula [M xRu1-x(terpy)2](PF6)2 (M = Fe, Co, II Ni, Cu), were prepared from solutions containing [M (terpy)2](PF6)2 and

[Ru(terpy)2](PF6)2 in equimolar ratios. Crystallisations were conducted using the slow evaporation method (1:1 MeCN:H2O). The cationic metal centre was the only difference between the complexes in each co-crystallisation experiment. The metal is completely shrouded by the ligand and therefore concealed from other complexes. This set of experiments was designed to test the effects of very small differences between complexes on the co-crystallisation process i.e. molecular recognition patterns between complexes that are chemically different but geometrically almost indistinguishable from one another.

*Size is an important factor because each measurement is statistically weighted equally and so for very large crystals their impact on the co-crystallisation system would be underestimated due to the amount of material consumed during the process. The opposite is true for very small crystals. Also, measuring a broken crystal could mean that particular crystal is measured more than once. This would also misrepresent the true range present in each batch. A record was kept of any measurements from crystals that were either broken, relatively large or small or of a different crystal habit and if the results from these were different from those obtained from regular co-crystals.

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Table 10 summarises the co-crystallisation experiments that will be discussed within this section and highlights all of the metal complexes involved, their colour and relative solution state concentrations (xsolution). The formula of the resulting co- crystals and their colour are also given. Each batch combination was conducted in triplicate to test reproducibility. This table summarises 12 co-crystallisation experiments. Ten co-crystals from each batch were analysed by SEM-EDX and the entire batch characterised by PXRD. Values such as MII:Ru ratios (MII is normalised to 1) and xsolid values are reported as xˉ ± s (xˉ = sample mean, s = sample standard deviation) in subsequent tables. For exact preparative experimental details, refer to Section 3.3.5.1.

Table 10: Summary of co-crystallisation experiments showing all metal complexes involved, their colours and relative solution concentration. The resulting co-crystal formula and colour are also shown.

Fraction of Complex A (colour) Complex B (red) A in solution Co-crystal formula (colour)

(xsolution)

[FexRu1-x(terpy)2](PF6)2 (dark [Fe(terpy)2](PF6)2 (purple) [Ru(terpy)2](PF6)2 0.50 purple)

[Co(terpy)2](PF6)2 (tan brown) [Ru(terpy)2](PF6)2 0.50 [CoxRu1-x(terpy)2](PF6)2 (red)

[Ni(terpy)2](PF6)2 (light brown) [Ru(terpy)2](PF6)2 0.50 [NixRu1-x(terpy)2](PF6)2 (red)

[Cu(terpy)2](PF6)2 (blue/green) [Ru(terpy)2](PF6)2 0.50 [CuxRu1-x(terpy)2](PF6)2 (red)

Figure 26 is an SEM secondary electron image* of representative co-crystals with the II general formula [M xRu1-x(terpy)2](PF6)2. The co-crystals shown in Figure 26 were found to have the general formula [CoxRu1-x(terpy)2](PF6)2 and were found to have II the typical thin sheet-like crystal habit exhibited by [M (terpy)2](PF6)2 crystals grown from MeCN:H2O solvent mixtures. Figure 27 shows the EDX spectrum of the red outlined area in Figure 26.

* An SEM secondary electron image is acquired using a secondary electron detector. This mode of imaging is mostly used to reveal the topographical intricacies of the surfaces being analysed.

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Figure 26: SEM secondary electron image of co-crystals with the general formula II [CoxRu1-x(terpy)2](PF6)2. Note the thin sheet-like crystal habit, which is typical for [M (terpy)2](PF6)2 complexes grown from this solvent mixture.

Formula

[Co0.52Ru0.48(terpy)2](PF6)2

Raw At% Ratio (Co) 1.02 0.52 (Ru) 0.95 0.48

Figure 27: EDX spectrum from the area outlined in red on the [CoxRu1-x(terpy)2](PF6)2 co-crystal shown in Figure 26. This co-crystal was found to contain 52% [Co(terpy)2](PF6)2 and 48% [Ru(terpy)2](PF6)2.

Representative SEM-EDX statistical data for these systems are summarised in Table 11, which shows the mean (xˉ), standard deviation (s), minimum (Min), maximum II (Max) and range for M xsolid values. The data in each row, determined by EDX, correspond to the element highlighted in bold. For example, the statistics for the system in the first row relate to the iron mole fraction relative to ruthenium in the solid state, whereas the values in the second row relate to the cobalt content relative to ruthenium.

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Table 11: Statistical summary of xsolid values obtained from EDX data for experiments resulting in II co-crystals with the general formula [M xRu1-x(terpy)2](PF6)2. The sample mean (xˉ), standard II deviation (s), minimum, maximum and range for M xsolid values are shown along with the co-crystal formula. The xsolid data correspond to the element in bold.

Co-crystallising systems xˉ(xsolid) s(xsolid) Minimum Maximum Range

[FexRu1-x(terpy)2](PF6)2 0.50 0.02 0.47 0.55 0.08

[CoxRu1-x(terpy)2](PF6)2 0.55 0.08 0.42 0.64 0.22

[NixRu1-x(terpy)2](PF6)2 0.55 0.07 0.43 0.67 0.24

[CuxRu1-x(terpy)2](PF6)2 0.51 0.08 0.41 0.62 0.21

II For all [M xRu1-x(terpy)2](PF6)2 systems discussed herein, measurements from irregular crystals such as that outlined by the white box in Figure 26 showed xsolid concentrations to be scattered within the ranges and not biased towards the upper or lower limits shown in Table 11.

Figure 28 is a colour-coded graphical representation of the same EDX information summarised in Table 11. The horizontal axis shows the different combinations of co-crystallised metal complexes and hence the metal ratios of interest and are labelled from left to right as Fe:Ru, Co:Ru, Ni:Ru and Cu:Ru. In addition, the measurements from each batch are labelled with the general formula i.e. measurements from the Co:Ru batch are labelled [CoxRu1-x(terpy)2](PF6)2. The y axis II is labelled M xsolid, thus for the Co:Ru system, this refers to the x variable in the

[CoxRu1-x(terpy)2](PF6)2 formula, and is the atomic fraction of Co detected in the solid by SEM-EDX. Note that the y axis has been expanded showing a range of 0.40-0.70 so that data points can be viewed with minimal overlap. It is important to note that data points of the same colour/shape represent measurements taken from any particular co-crystal within a co-crystallisation batch. So for example, the data points outlined by the red box, are from a different co-crystal to those outlined by the black box, but both sets of measurements were from co-crystals grown from the same solution.

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II EDX GRAPHICAL SUMMARY: [M xRu1-x(terpy)2](PF6)2 from 0.50:0.50 solutions 0.70

[NixRu1-x(terpy)2](PF6)2

[Co Ru (terpy) ](PF ) 0.65 x 1-x 2 6 2

[CuxRu1-x(terpy)2](PF6)2

0.60

[FexRu1-x(terpy)2](PF6)2

solid solid x

x 0.55

II II

M M

0.50

0.45

0.40 0.00 Fe:Ru0.10 Co:Ru0.20 Ni:Ru0.30 Cu:Ru0.40 0.50 Co-crystallisation experiment

Figure 28: Colour-coded plot of EDX results of co-crystals of the general formula II [M xRu1-x(terpy)2](PF6)2. The horizontal axis shows the metal ratios of interest and are labelled from II left to right as Fe:Ru, Co:Ru, Ni:Ru and Cu:Ru. The y axis is labelled M xsolid, thus for the Co:Ru system, this refers to the x variable in the [CoxRu1-x(terpy)2](PF6)2 formula, and is the atomic fraction of Co detected in the solid by SEM-EDX. Data points of the same colour/shape represent measurements taken from any particular co-crystal within a co-crystallisation batch.

Several observations can be made from the data presented in Figure 28 and Table 11. II It is apparent that the different batches of [M xRu1-x(terpy)2](PF6)2 co-crystals share many similarities. The first and perhaps most noticeable, is that the measured xsolid values are different for co-crystals grown from the same batch, such that xsolid single co- crystal 1 ≠ xsolid single co-crystal 2. So for example in Figure 28, the measurements enclosed in the red box have an average xsolid value of 0.51 (i.e. this co-crystal had an average of 51% [Co(terpy)2](PF6)2); compared to the measurements enclosed in the black box, which have an average xsolid value of 0.47. These data are consistent with observations made from previously conducted experiments, which showed that co-crystals grown from solutions containing equimolar ratio of metal complexes of A B the type [M xM 1-x(terpy)2](PF6)2 can have a range of concentrations. As already mentioned, experiments of this type were previously conducted, however a record was not kept of which measurement originated from which co-crystal. The new results show that measurements made from a single co-crystal are clustered together, with respect to the MII:Ru ratio (within 2.5%) and thus illustrates that allowing for instrumental error, the individual co-crystals are homogeneous.

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II II Statistically, the average [M (terpy)2](PF6)2 (M = Fe, Co, Ni Cu) mole fractions

(xsolid) for all of the co-crystallisation experiments were found to be at or around

0.50. The minimum and maximum xsolid values were found to be within two standard deviations of the mean in all four types of experiment. For each of the four experiments shown in Figure 28, the data points are distributed above and below 0.50. This indicates, that under these crystallising conditions, each of the II [M (terpy)2](PF6)2 complexes has a similar solubility to [Ru(terpy)2](PF6)2. If complex A were less soluble than complex B (or vice versa) then complex A would crystallise first with some of complex B. As crystallisation progresses, the relative concentration of complex A in solution would decrease. As the relative concentration of each complex in solution is constantly changing, the ratio of the two complexes in the co-crystals during crystal growth also changes. This leads to the formation of co-crystals with a concentration gradient, where higher concentrations of complex B to relative to complex A are present on the co-crystal’s surface compared to the ratios present towards the co-crystal’s nucleus. SEM-EDX analysis of co-crystals with solubility gradients would yield xsolid values above or below that of 0.50 but not both.

Earlier it was mentioned that SEM-EDX is largely a surface technique, capable of measuring to depths of about 5 μm for these types of materials. As part of the protocol developed during this project, representative co-crystals that already had been analysed were crushed and re-prepared for SEM-EDX analysis. Comparisons between measurements made on crushed and intact (surface) co-crystals consistently showed only small differences (± 0.03). This is further evidence that the complexes in each of the crystallising solutions have similar solubilities and that co-crystals of II the formula [M xRu1-x(terpy)2](PF6)2 that grow from these solutions do not have concentration gradients. Overall, the results presented here indicate that the variation in xsolid values between co-crystals grown from the same batch was due to supramolecular selection.

Supramolecular selection is thought to proceed through molecular recognition mechanisms whereby intermolecular interactions between like complexes are slightly favoured over interactions between different complexes. Structural differences between complexes, such as their size and shape, are likely factors that may play a

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CHAPTER 4 role during the selection process and therefore influence crystal packing. Although metal complexes have no defined widths and heights, their dimensions may be measured using the interpretation shown in Figure 29. Using this three-dimensional 2+ graphical representation as a guide, the dimensions of [M(terpyR)2] molecules in reported CSD crystal structures were measured. Figure 30 is a colour-coded scatter plot showing the measured widths on the x axis versus heights on the y axis (in Å) of these metal complexes.

S4 axis

Width 4-C  4′′-C

H, OH

Height 4′-C  4′-C

z+ Figure 29: A three-dimensional illustration of a [M(terpyR)2] complex showing the orthogonal relationship between the two ligands. The width is interpreted to be the distance between the 4-carbon and 4′′-carbon atoms on the same ligand (black lines), while the height is taken to be the distance between the 4′-carbon atoms on the two ligands (red lines). The S4 axis is shown by the vertical dotted line.

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2+ Width vs. height of [M(terpyR)2] in reported crystal structures 9.70 2+ [Co(terpy)2]2+[Co(terpy)2] 2+ [Co(terpyOH)2]2+[Co(terpyO)(terpyOH)] 2+ 9.60 [Cu(terpy)2]2+[Cu(terpy)2] 2+ [Cu(terpyOH)2]2+[Cu(terpyOH)2] 2+ [Fe(terpy)[Fe(terpy)2]2+2] 2+ 9.50 [Fe(terpyOH)[Fe(terpyOH)2]2+2] 2+ [Ni(terpy)2]2+[Ni(terpy)2]

2+ [Ni(terpyOH)2]2+[Ni(terpyOH)2] 9.40 2+ [Ru(terpy)2]2+[Ru(terpy)2] 2+ Height (Å)Height [Ru(terpyOH)2]2+[Ru(terpyOH)2] Line of best fit 9.30

9.20

9.10 9.15 9.20 9.25 9.30 9.35 9.40 9.45 9.50 Width (Å) 2+ Figure 30: Width and Height of various [M(terpyR)2] complexes reported in the CSD. The solid line represents the line of best fit. The blue boxes formally segregate the data points according to visually observed clustering. Structures appear more than once due to different counterions, solvates and data collection temperatures.

The data points in Figure 30 can be loosely separated by eye into two clusters. The 2+ first is more localised at the lower end of the scale and contains [Fe(terpy)2] 2+ (orange markers), [Fe(terpyOH)2] (khaki green markers) and a few points 2+ 2+ * belonging to [Co(terpy)2] and [Co(terpyO)(terpyOH)] . The second cluster is much larger and more dispersed and contains data points belonging to all but Fe2+ metal complexes. The data points within this very loose cluster are so close together that without colour it would be extremely difficult to assign data points to the various metal complex species. Regardless of this approximate grouping, all the points in this scatter plot are within 0.25 Å in width and 0.44 Å in height of each other, which translate to an average of 2.5% and 4.5% of a complex’s interpreted width and height respectively. These values demonstrate just how similar in size these metal complexes are to one another and so conceivably, a slight difference in overall structure and perhaps functionality is enough to trigger the postulated selective

* These [Co(terpyO)(terpyOH)]2+ metal complexes are known to be Co3+ complexes, which are smaller than Co2+ complexes.

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CHAPTER 4 behaviour, which gives rise to the observed data. The size and shape of metal complexes are known to be influenced by factors such as those listed in Table 12.

Table 12: Comparison of factors that are known to influence metal complex size and shape.

Metal Fe Co Ni Cu Ru Oxidation number II II II II II Spin state* LS HS N/A N/A LS d electron configuration d6 d7 d8 d9 d6 Unpaired electrons 0 3 2 1 0 Jahn-Teller distortion No No No Yes No * II 2+ 56,308 Spin states typical for [M (terpy)2] complexes.

Combining the SEM-EDX data with the information presented in Table 12, there is no obvious pattern to explain the results obtained. In the SEM-EDX plot (Figure 28), the data for the [CuxRu1-x(terpy)2](PF6)2 combination has a similar scatter to the co-crystals in the [CoxRu1-x(terpy)2](PF6)2 and [NixRu1-x(terpy)2](PF6)2 batches (xsolid ranges of ca. 0.22). Octahedral complexes that contain Cu2+, a d9 metal cation are expected to display a distorted geometry attributed to the Jahn-Teller effect, while II 2+ 2+ 2+ [M (terpy)2] octahedral complexes of Co and Ni , d7 and d8 metal cations respectively, are not. Based on the similarities of the SEM-EDX data for the II II [M xRu1-x(terpy)2](PF6)2 systems (M = Co, Ni, Cu), Jahn-Teller distortions alone are not thought to be a major influence on co-crystallisation behaviour for these experiments and the resulting spread in the xsolid values. The range of xsolid values for II the [FexRu1-x(terpy)2](PF6)2 system was found to be much smaller than when M = Co, Ni, Cu. Overall, according to the information in Table 12, it appears that more similarities exist between Ru2+ and Fe2+ complexes than with complexes of the other metal cations. These are some of the possible reasons why the xsolid values for the

[FexRu1-x(terpy)2](PF6)2 system were less scattered than the xsolid values for the other II [M xRu1-x(terpy)2](PF6)2 systems.

Therefore, the observed SEM-EDX results could be attributed to the size and shape of relative complex species as influenced by subtle differences in structure, which affect the intermolecular interactions between complexes and consequently how well the two molecules can differentiate one another through molecular recognition processes. Varying levels of differences between complexes that are still able to form

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CHAPTER 4 co-crystals would lead to varying degrees of the supramolecular selection observed, i.e. the range of xsolid values between co-crystals grown from the same batch.

The reasoning that co-crystallisation depends on molecular recognition between complexes is ultimately based on the favourability of intermolecular interactions between like complexes over those between complexes that are slightly different from one another. The study of these interactions in the crystalline state is best facilitated by the collection of SCXRD data. Unfortunately, the single co-crystals obtained diffracted poorly due to their thin crystal habit. In lieu of crystal structures, powder XRD, which is a bulk property analytical technique, was conducted on pure and co-crystallised samples. Where possible, structural information was inferred using powder diffraction patterns simulated from known single crystal structures, for which crystallographic data is available in the CSD.51

II All powder diffraction samples within this [M (terpy)2](PF6)2 series were prepared as thin films and analysed at room temperature (data collected to up to 60°2θ) with an incident X-ray radiation sourced from a line-focused copper (Cu) X-ray tube (1.54060 Å). Powder XRD patterns for this and all subsequent series are graphed so that the position °2θ (shown on the x axis) is plotted against the relative intensity “counts” (shown on the y axis). Powder XRD of these types of materials usually produces patterns with one or two very intense low angle peaks. Therefore, individual patterns are magnified to highlight less intense higher angle reflections. Sometimes the intensity of these peaks is so much greater than the other reflections that it becomes necessary to exclude their peak maxima in order to observe the remainder of the pattern.

II II Diffraction patterns of freshly prepared pure [M (terpy)2](PF6)2 crystals (M = Fe, Co, Ni, Cu, Ru) are shown in Figure 31. Also shown in this figure (first pattern from the top), is a simulated trace calculated from a published crystal structure of

[Cu(terpy)2](PF6)2 grown from acetone, which was collected at room temperature and deposited in the CSD (reference code BEJPUB).309 Miller indices have been II II assigned to the peaks of [M (terpy)2](PF6)2 (M = Co, Ni, Cu) based on the indexing of the simulated pattern; their positions are represented by dotted lines. There were

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CHAPTER 4 no simulated patterns that matched those obtained experimentally for

[Fe(terpy)2](PF6)2 and [Ru(terpy)2](PF6)2 published in the CSD.

II II PXRD: [M (terpy)2](PF6)2 (M = Fe, Co, Ni, Cu, Ru) 35000 104 and 200 101

112 212 30000 211 BEJPUB (P421c) 102 210 [Cu(terpy)2](PF6)2 002 110 004 202

25000

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0 55 1010 1515 2020 2525 3030 Position [°2θ (Cu)]

II II Figure 31: Powder XRD patterns of freshly prepared pure [M (terpy)2](PF6)2 crystals ( M = Fe, Co, Ni, Cu, Ru). The first diffraction pattern from the top is a simulated trace calculated from a published 309 crystal structure of [Cu(terpy)2](PF6)2 deposited in the CSD (reference code BEJPUB). Miller II II indices have been assigned to the peaks of [M (terpy)2](PF6)2 (M = Co, Ni, Cu) based on the indexing of the calculated pattern. Although not clear from this plot, the [101] reflection at around 10°2θ, which is present in the three isomorphous and simulated powder patterns, is a single peak that shows no evidence of any underlying peaks.

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The simulated pattern of the solvent free [Cu(terpy)2](PF6)2 reported structure, (CSD reference code BEJPUB),309 correlates well in regards to peak position and relative peak intensity with the [Cu(terpy)2](PF6)2 experimental pattern. Although the two compounds were recrystallised from different solvent mixtures, it appears that at room temperature the experimentally obtained [Cu(terpy)2](PF6)2 is isomorphous with the structure reported by Declercq et al. The experimental powder patterns of

[Co(terpy)2](PF6)2 and [Ni(terpy)2](PF6)2 match that of [Cu(terpy)2](PF6)2 and therefore all three are isomorphous, belonging to the P4¯21c primitive tetragonal space group.

It is important to note that peaks shift according to Bragg’s Law with changes in lattice dimensions. Changes in these dimensions sometimes cause overlapping reflections to resolve. Leftward peak shifts signify elongated lattice dimensions while rightward shifts indicate shortened lattice parameters. Therefore, two patterns obtained from isomorphous compounds each with slightly different lattice dimensions could have a different number of observed peaks. An example of this is observed for the simulated pattern in Figure 31. Upon initial inspection, the simulated pattern appears to be comprised of only well resolved reflections without any peak overlap. However, after a more in-depth analysis of this calculated pattern, the reflection at around 20°2θ was found to be an overlap of the [104] and [200] reflections; these two peaks are of similar intensity, have the same d spacing (4.465 Å) and are only separated by a one thousandth of a °2θ. The overlap is most noticeable in the collected [Cu(terpy)2](PF6)2 pattern, where the peak maxima are separated by 0.25°2θ and to a lesser extent in the [Ni(terpy)2](PF6)2 pattern.

Magnification of this peak in the [Co(terpy)2](PF6)2 pattern shows evidence of a shoulder on the right hand side, which is likely to be the shift of the [200] reflection.

Another observation, which becomes more apparent due to the dotted lines, are the very slight rightward shifts of the [002] and [004] reflections in the collected patterns from their positions in the simulated trace (by 0.12 and 0.24°2θ respectively). This shift possibly indicates a tightening of the d002 and d004 spacings, causing a very slight shortening of the c-axis lattice parameter in accordance with Bragg’s law. Apart from these observations, it appears that the unit cell dimensions for the

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II II [M (terpy)2](PF6)2 (M = Co, Ni, Cu) crystals are identical to or vary only slightly from the published BEJPUB structure (a = 8.930(3), b = 8.930(3), c = 20.623(5)).309

As there were no simulated powder patterns found in the CSD that matched those experimentally obtained at room temperature for [Fe(terpy)2](PF6)2 and

[Ru(terpy)2](PF6)2, absolute conclusions regarding structure cannot be made without the collection of single crystal data. However, it may be inferred that of all the patterns shown in Figure 31, the [Fe(terpy)2](PF6)2 lattice possesses the least amount of symmetry at room temperature because the powder pattern consists of the greatest number of peaks. On the contrary, the [Ru(terpy)2](PF6)2 powder pattern shows very few peaks, and therefore is expected to belong to a high symmetry space group at room temperature. These conclusions regarding symmetry are drawn based on the assumption that powder patterns of these crystals indicate the presence of a single phase.* Furthermore and perhaps most noteworthy in regards to phase identification of co-crystalline samples, is the difference of the [Ru(terpy)2](PF6)2 pattern compared with the experimental patterns of the other four compounds. Comparison of the experimental patterns shown in Figure 31 reveals that all the peaks associated with the [Ru(terpy)2](PF6)2 occur at unique positions that avoid overlap with the other powder patterns. Therefore, if a diffraction pattern of any co-crystal system exhibits a peak at or around 7.8°2θ, it can likely be attributed to an inclusion of the

[Ru(terpy)2](PF6)2 phase in the bulk sample.

It is unfortunate that SCXRD data could not be collected for any of the compounds within this series; however, a great deal of information can be extracted from the comparison between the powder patterns of the co-crystals and their corresponding pure compounds. It was hypothesised that since the pure structures of II II [M (terpy)2](PF6)2 (M = Co, Ni, Cu) were found to be isomorphous, the structures II II of [M xRu1-x(terpy)2](PF6)2 (M = Co, Ni, Cu) would also be isomorphous.

Figure 32 - Figure 36 show representative powder diffraction patterns of the various II II [M xRu1-x(terpy)2](PF6)2 co-crystals (M = Fe, Co, Ni, Cu) that were co-crystallised

* Powder XRD of [Fe(terpy)2](PF6)2 and [Ru(terpy)2](PF6)2 was repeated twice more on new batches of freshly recrystallised samples to test for multiple phases, as verification using simulated patterns was not available. The results were found to be reproducible, suggesting the presence of a single phase.

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II from solutions containing [M (terpy)2](PF6)2 and [Ru(terpy)2](PF6)2 in equimolar ratios. In each of these following figures the co-crystal pattern is shown between the II [M (terpy)2](PF6)2 pattern (top) and [Ru(terpy)2](PF6)2 (bottom). The diffraction patterns of the co-crystals are coloured differently to facilitate the comparison between the various patterns. Dotted lines and shaded areas emphasise the differences and similarities between patterns.

PXRD: [FexRu1-x(terpy)2](PF6)2 co-crystals

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Figure 32: Powder XRD patterns of freshly prepared [FexRu1-x(terpy)2](PF6)2 co-crystals (shown in purple) with the diffraction patterns of [Fe(terpy)2](PF6)2 (top) and [Ru(terpy)2](PF6)2 (bottom). Dotted lines and shaded areas emphasise the differences between like patterns.

By examining the data presented in Figure 32, it is obvious that none of the peaks in the [Ru(terpy)2](PF6)2 phase are present in the purple pattern. The general profiles of both the [FexRu1-x(terpy)2](PF6)2 and [Fe(terpy)2](PF6)2 patterns are similar in most cases. The reflections at 13.3, 17.8, 18.5, 20.4 and 26.8°2θ that are present in the

[Fe(terpy)2](PF6)2 pattern, have shifted to the left in the [FexRu1-x(terpy)2](PF6)2 pattern by 0.2°2θ. In the co-crystal pattern, the reflection at 8.8°2θ now shows a prominent shoulder. Without hkl indexing, it is unclear if this weak reflection was present as an underlying peak in the [Fe(terpy)2](PF6)2 pattern. The shoulder at

14.8°2θ, which is visible in the [Fe(terpy)2](PF6)2 pattern, seems to have merged with its more intense neighbour and is absent from the co-crystal diffraction profile. Similarly, the slight leftward shift of the peak at 26.8°2θ seems to have led to the coalescence of the two peaks highlighted in this area. The leftward shifts indicate a 2+ slight expansion of the unit cell due to the inclusion of the larger [Ru(terpy)2]

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complex into the [Fe(terpy)2](PF6)2 phase. This is a reasonable conclusion as a size difference between these two complexes is indicated in the size chart shown in Figure 30. It is interesting to note that the leftward shifts of only a selected number of peaks are observed as opposed to a complete transposition of the entire co-crystal pattern. This suggests a lattice expansion in only one or two dimensions. Overall, there is overwhelming evidence to support the conclusion that

[FexRu1-x(terpy)2](PF6)2 co-crystals are exclusively comprised of the

[Fe(terpy)2](PF6)2 phase, albeit in a slightly elongated lattice. Therefore, the single crystal SEM-EDX findings seem to be representative of the bulk sample.

The powder XRD pattern of [CoxRu1-x(terpy)2](PF6)2 together with the patterns of

[Co(terpy)2](PF6)2 and [Ru(terpy)2](PF6)2 are shown in Figure 33.

PXRD: [CoxRu1-x(terpy)2](PF6)2 co-crystals

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8000 [Co(terpy)2](PF6)2 7000

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Figure 33: Powder XRD patterns of freshly prepared [CoxRu1-x(terpy)2](PF6)2 co-crystals (shown in blue) with the diffraction patterns of [Co(terpy)2](PF6)2 (top) and [Ru(terpy)2](PF6)2 (bottom). Dotted lines and shaded areas emphasise the differences between like patterns.

Peaks associated with the [Ru(terpy)2](PF6)2 phase are absent in the

[CoxRu1-x(terpy)2](PF6)2 pattern. None of the patterns simulated from literature single crystal structures match the [CoxRu1-x(terpy)2](PF6)2 pattern shown in Figure 33. Unlike the observation made for the previous set of results (Figure 32), only a few similarities are noted between the patterns of [CoxRu1-x(terpy)2](PF6)2 and

[Co(terpy)2](PF6)2. The dotted lines at around 10.7, 13.3 and 22.7°2θ show the possible similarities between the two patterns. The shaded peaks at around 10.7°2θ

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and 22.7°2θ could be due to the [Co(terpy)2](PF6)2 phase or the result of the formation of a completely new structure. The shaded peak at around 16.5°2θ suggests the latter. If the [Co(terpy)2](PF6)2 phase is indeed present in the co-crystalline pattern then the peaks at around 20.0°2θ could be the separation of the [104] and [200] reflections due to the differences in the lattice parameters in the

[CoxRu1-x(terpy)2](PF6)2 structure compared to the structure of pure

[Co(terpy)2](PF6)2. Since none of these peaks occur at exactly the same positions in both patterns, it is unlikely that pure [Co(terpy)2](PF6)2 crystals formed during co-crystallisation. Overall, there is evidence to support the conclusion that most

[CoxRu1-x(terpy)2](PF6)2 co-crystals have adopted a new structure and some evidence to support the inference that a small percentage have formed in the

[Co(terpy)2](PF6)2 phase.

The powder XRD pattern of [NixRu1-x(terpy)2](PF6)2 together with the patterns of

[Ni(terpy)2](PF6)2 and [Ru(terpy)2](PF6)2 are shown in Figure 34. Upon examination of the [NixRu1-x(terpy)2](PF6)2 XRD pattern, it was immediately noted that the pattern for this batch of co-crystals greatly resembled the pattern of

[CoxRu1-x(terpy)2](PF6)2. The [CoxRu1-x(terpy)2](PF6)2 and [NixRu1-x(terpy)2](PF6)2 powder patterns are shown in Figure 35.

PXRD: [NixRu1-x(terpy)2](PF6)2 co-crystals

9000

8000 [Ni(terpy)2](PF6)2 7000

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5000 [NixRu1-x(terpy)2](PF6)2

4000

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Counts Counts 2000

1000 [Ru(terpy)2](PF6)2

0 5 1010 1515 2020 2525 3030 Position [°2θ (Cu)]

Figure 34: Powder XRD patterns of freshly prepared [NixRu1-x(terpy)2](PF6)2 co-crystals (shown in green) with the diffraction patterns of [Ni(terpy)2](PF6)2 (top) and [Ru(terpy)2](PF6)2 (bottom). Dotted lines and shaded areas emphasise the differences between like patterns.

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II II PXRD: [M xRu1-x(terpy)2](PF6)2 co-crystals (M = Co, Ni)

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8000 [NixRu1-x(terpy)2](PF6)2 7000

6000

5000

4000

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Counts Counts 2000 [CoxRu1-x(terpy)2](PF6)2

1000

0 55 1010 1515 2020 2525 3030 Position [°2θ (Cu)]

Figure 35: Powder XRD patterns of freshly prepared [CoxRu1-x(terpy)2](PF6)2 co-crystals (shown in blue) and [NixRu1-x(terpy)2](PF6)2 co-crystals (shown in green). Dotted lines and shaded areas are present to emphasise the variations between these patterns.

The peaks in the [NixRu1-x(terpy)2](PF6)2 pattern correlate well to the peaks in the

[CoxRu1-x(terpy)2](PF6)2 pattern except in the areas highlighted by the green shading, which may indicate the possibility of a phase impurity. These differences could also be attributed to subtle differences in the lattice parameters between

[NixRu1-x(terpy)2](PF6)2 and [CoxRu1-x(terpy)2](PF6)2 co-crystals as each highlighted peak is adjacent to a more intense peak. Since the two patterns shown in Figure 35 are otherwise almost identical, it is very likely that most of the

[NixRu1-x(terpy)2](PF6)2 co-crystals are isomorphous with [CoxRu1-x(terpy)2](PF6)2.

Furthermore, due to the similarities between the patterns of [CoxRu1-x(terpy)2](PF6)2 and [NixRu1-x(terpy)2](PF6)2, the proposal that [CoxRu1-x(terpy)2](PF6)2 was contaminated with the [Co(terpy)2](PF6)2 phase is unlikely. Therefore, the majority of co-crystals resulting from these experiments seem to have formed a completely new crystalline phase in the absence of any major phase impurities.

The last set of powder patterns to be discussed in this section are those pertaining to the [CuxRu1-x(terpy)2](PF6)2 system. The co-crystal diffraction pattern along with the patterns of [Cu(terpy)2](PF6)2 and [Ru(terpy)2](PF6)2 are shown in Figure 36.

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PXRD: [CuxRu1-x(terpy)2](PF6)2 co-crystals

9000 [Cu(terpy)2](PF6)2 8000

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4000

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0 55 1010 1515 2020 25 3030 Position [°2θ (Cu)]

Figure 36: Powder XRD patterns of freshly prepared [CuxRu1-x(terpy)2](PF6)2 co-crystals (shown in red) with the diffraction patterns of [Cu(terpy)2](PF6)2 (top) and [Ru(terpy)2](PF6)2 (bottom). Dotted lines and shaded areas emphasise the differences between like patterns.

In keeping with the trend observed thus far, the main peaks from the

[Ru(terpy)2](PF6)2 phase are absent in the co-crystal pattern. The only notable differences observed between the patterns of [CuxRu1-x(terpy)2](PF6)2 and

[Cu(terpy)2](PF6)2 are highlighted in red at around 10.8, 14.1 and 26.1°2θ. Overall the [CuxRu1-x(terpy)2](PF6)2 pattern looks very similar to that of [Cu(terpy)2](PF6)2. The peak highlighted at 14.1°2θ is present but very weak in the

[CuxRu1-x(terpy)2](PF6)2 pattern. The peaks highlighted at 26.1°2θ are also common to both patterns however they are relatively weaker in the [Cu(terpy)2](PF6)2 pattern. The difference in relative peak intensity can be attributed to preferred orientation effects, which are common for highly crystalline samples such as these.* The difference in the intensities is more obvious for the peak at 8.7°2θ, which is visible in both patterns but has a much greater relative intensity in the [CuxRu1-x(terpy)2](PF6)2 pattern. The extra peaks in the shaded area around 10.8°2θ in the

[CuxRu1-x(terpy)2](PF6)2 pattern could either be due to preferred orientation or a slight phase impurity. Overall, the data suggests that a most of the co-crystals in the bulk [CuxRu1-x(terpy)2](PF6)2 sample adopted the [Cu(terpy)2](PF6)2 phase.

*Ideally, every possible crystalline orientation is represented equally resulting in a true average. For samples that display preferred orientation the average is skewed by one or more crystalline orientations, which in turn distorts the relative intensities.

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II 4.3.2 [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystallisation systems

II Several co-crystals with the general formula [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 II II (M = Fe, Ni, Cu) were prepared from solutions containing [M (terpyOH)2](BF4)2 and [Ru(terpy)2](BF4)2 in 0.50:0.50 and 0.05:0.95 ratios. Crystallisations were conducted using the slow evaporation method (1:1 MeCN:H2O). Each experiment combination involves complexes that are chemically and structurally different (i.e. different metal centres and ligands) but still which form the 2D terpy embrace motif. These experiments were designed to test the effects of larger differences between complexes on co-crystallisation.

In addition to these combinations, a co-crystallisation solution was prepared that contained an equimolar ratio of [Ru(terpy)2](BF4)2 and III [Co (terpyO)(terpyOH)](BF4)2. Unlike the metal complexes in II II [M (terpyOH)2](BF4)2 crystals (M = Fe, Ni, Cu), which form π-interactions to yield III the 2D terpy motif, the molecules in [Co (terpyO)(terpyOH)](BF4)2 predominately interact through hydrogen bonds (no π-interactions between complexes) to form a hydrogen bond motif.34 This experiment was conducted to test whether co-crystallisation would force [CoIII(terpyO)(terpyOH)]2+ into a non hydrogen 2+ bonding lattice or [Ru(terpy)2] complexes (which cannot form hydrogen bonds) into the hydrogen bond motif.

Table 13 summarises the co-crystallisation experiments that will be discussed within this section and highlights all of the metal complexes involved, their colour and relative solution state concentrations (xsolution). The formulae of the resulting co-crystals and their colour are also given. For simplicity, the formulae of the various pure complexes and co-crystals are shown unsolvated, however most contain at least one molecule of water per metal complex unit (as determined from XRD data). Each batch combination was conducted in triplicate to test reproducibility. This table summarises 21 co-crystallisation experiments. Ten co-crystals from each batch were analysed by SEM-EDX. Values such as MII:Ru ratios (where the MII is normalised to 1) and xsolid values are reported as xˉ ± s (xˉ = sample mean; s = sample standard deviation). Single crystal and powder XRD data were collected from batches that

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CHAPTER 4 produced co-crystals (as determined by SEM-EDX). For exact preparative experimental details refer to Section 3.3.5.1.

Table 13: Summary of co-crystallisation experiments showing all metal complexes involved, their colour and relative solution concentrations. The resulting co-crystal formula and colour are also shown.

Fraction of Complex A (colour) Complex B (red) A in solution Co-crystal formula (colour)

(xsolution)

[Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 [Fe(terpyOH)2](BF4)2 (purple) [Ru(terpy)2](BF4)2 0.50, 0.05 (dark purple) III [Co (terpyO)(terpyOH)](BF4)2 [Ru(terpy)2](BF4)2 0.50 No co-crystallisation (brown) [Ni(terpyOH) ] [Ru(terpy) ] (BF ) [Ni(terpyOH)2](BF4)2 (brown) [Ru(terpy)2](BF4)2 0.50, 0.05 2 x 2 1-x 4 2 (red) [Cu(terpyOH) ] [Ru(terpy) ] (BF ) [Cu(terpyOH)2](BF4)2 (blue) [Ru(terpy)2](BF4)2 0.50, 0.05 2 x 2 1-x 4 2 (red)

Co-crystals resulting from these experiments all exhibited similar crystal habits. Figure 37 and Figure 38 show the SEM secondary electron images of representative II II co-crystals with the general formula [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (M = Fe, Ni, Cu) showing the rectangular prism habit. Looking at the co-crystals in the secondary electron images, there also seems to be some fine topological striations and surface irregularities. Figure 38 compares the secondary electron and * backscattered images of a [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystal. The subtle striations seen in the secondary electron image are also visible in the backscattered image. Therefore, the subtle differences in shading in the backscattered image are likely due to changes in the local angle of backscatter. Overall, the appearance of the surface of the [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystal shown in the backscattered image (i.e. visual contrast between various areas) suggests that the concentration of the two complexes varies very little over the surface.

*Backscattered images are used to differentiate between areas of different electron density. Heavier elements such as Ru have more electrons than lighter elements such as first row transition metals and as a result, Ru-rich areas appear brighter. Thus, the visual contrast between areas is qualitatively indicative of chemical composition.

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Although beyond the capabilities of the instrument used, it would be interesting to examine the surface feratures of these types of co-crystals at lower voltages (ca. 10kV).

Figure 37: Secondary electron SEM images of co-crystals with the formula [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (left) and [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (right). Note the co-crystals share similar dimensions and have a comparable rectangular prism crystal habit.

Figure 38: Secondary electron (left) and backscattered (right) SEM images of a co-crystal with the formula [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2.

Figure 39 shows an SEM secondary electron image of crystals grown from a solution III containing an equimolar ratio of [Co (terpyO)(terpyOH)](BF4)2 and

[Ru(terpy)2](BF4)2. The thin sheets such as the one outlined in red were found to contain only [Ru(terpy)2](BF4)2. The multifaceted prisms (outlined in yellow) were III found to be exclusively composed of [Co (terpyO)(terpyOH)](BF4)2. Repeated attempts to co-crystallise the two complexes were unsuccessful as each experiment resulted in a sample containing only pure crystals of both complexes, each with a different habit. It appears that the supramolecular interactions of these two complexes are too different to allow the complexes to co-crystallise. Although the overall shape of the [CoIII(terpyO)(terpyOH)]2+ complex lends itself to π-interactions

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CHAPTER 4 and hence formation of the 2D terpy embrace, these results strongly suggest that no 2+ such interactions occurred. Similarly, the results suggest that the [Ru(terpy)2] complex, which is unable to form hydrogen bonds due to an absence of a hydroxyl group, could not be accommodated into the hydrogen bond motif.

Figure 39: SEM image of crystals grown from a solution containing a 1:1 ratio of III [Co (terpyO)(terpyOH)](BF4)2 and [Ru(terpy)2](BF4)2. The image shows crystals of two distinct habits. The large plates/sheets (outlined in red) were found to contain only [Ru(terpy)2](BF4)2 while III the prisms (outlined in yellow) were found to only contain [Co (terpyO)(terpyOH)](BF4)2.

Representative SEM-EDX statistical data for co-crystals formed from solutions II containing 50% [M (terpyOH)2](BF4)2 is summarised in Table 14, which shows the mean (xˉ), standard deviation (s), minimum (Min), maximum (Max) and range for MII xsolid values. The data in each row, determined by EDX, correspond to the element highlighted in bold. For example, the statistics for the system in the first row relate to the mole fraction of iron relative to that of ruthenium in the solid state, whereas the values in the second row relate to the nickel content relative to ruthenium.

Table 14: Statistical summary of xsolid values obtained from EDX data for experiments resulting in II co-crystals with the general formula [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 that were formed from II solutions containing 50% [M (terpyOH)2](BF4)2. The sample mean (xˉ), standard deviation (s), II minimum, maximum and range for M xsolid values are shown along with the co-crystal formula. The xsolid data corresponds to the element in bold.

Co-crystallising systems xˉ(xsolid) s(xsolid) Minimum Maximum Range

[Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 0.55 0.03 0.51 0.60 0.09

[Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 0.54 0.06 0.47 0.65 0.18

[Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 0.54 0.02 0.49 0.58 0.09

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Figure 40 is a colour-coded graphical representation of the same EDX information summarised in Table 14. The horizontal axis shows the different combinations of co-crystallised metal complexes and hence the metal ratios of interest and are labelled from left to right as Fe:Ru, Ni:Ru and Cu:Ru. In addition, the data points from each batch are labelled with the general formula, i.e. measurements from the

Cu:Ru batch are labelled [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2. The primary y axis II on the left is labelled M xsolid. Thus for the Cu:Ru system, this refers to the x variable in the [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystal formula, and is the atomic fraction of Cu detected in the solid by SEM-EDX. It is important to note that all measurements taken from a single co-crystal (at least three) within a co-crystallisation batch are represented by one type of marker. So for example, the

[Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 data points outlined by the blue box, are from a different co-crystal to those outlined by the black box, but both sets of measurements were from co-crystals grown from the same solution. The secondary y axis on the II right is labelled M xsolid (mother liquor residue) and corresponds to the red data points outlined in the red box. These data points refer to the atomic fraction of MII detected in the residue resulting from the evaporation of the mother liquor after the co-crystals were harvested. The error bars associated with these red markers correspond to one standard deviation.

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II EDX GRAPHICAL SUMMARY: [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 from 0.50:0.50 solutions 0.650.65 0.75

0.70

[Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 [Cu(terpyOH) ] [Ru(terpy) ] (BF ) 2 x 2 1-x 4 2 0.65 0.600.60 0.60

0.55 [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 0.55

0.55 0.50

solid solid x

x 0.45

II II M M 0.40

0.500.50 0.40

(mother liquor residue) residue) liquor liquor (mother (mother

0.35

solid solid

x x II

0.30 II M 0.450.45 M 0.25

0.20

0.400.40 0.15 0 Fe:Ru0.1 Ni:Ru0.2 Cu:Ru0.3 0.4 Co-crystallisation experiment

Figure 40: Colour-coded plot of EDX results of co-crystals of the general formula II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2. The horizontal axis shows the metal ratios of interest and are labelled from left to right as Fe:Ru, Ni:Ru and Cu:Ru. The primary y axis on the left is labelled MII II xsolid, and corresponds to the atomic fraction of M detected in the solid by SEM-EDX. The secondary II y axis on the right is labelled M xsolid (mother liquor residue) and corresponds to the red data points outlined in the red box. These data points refer to the atomic fraction of MII detected in the residue resulting from the evaporation of the mother liquor after the co-crystals were harvested. The error bars associated with these markers correspond to one standard deviation.

Several key pieces of information can be extracted from the data presented in Table 14 and Figure 40. The data points from the same co-crystal are clustered together giving an intracrystal xsolid variance of no more than ± 0.03. These results show that allowing for instrumental error, the ratio of the two complexes in each single co-crystal varies very little over the areas measured. However, the average xsolid values from different co-crystals grown from the same solution vary by up to 0.13, such that xsolid single co-crystal 1 ≠ xsolid single co-crystal 2. So for example in Figure 40, the measurements enclosed in the black box have an average xsolid value of 0.54, i.e. this co-crystal had an average of 54% [Cu(terpyOH)2](BF4)2; compare to the measurements enclosed in the blue box, which have an average xsolid value of 0.50. These data indicate that co-crystals of the formula II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 grown from the same solution can have a II range of [M (terpyOH)2](BF4)2 concentrations relative to [Ru(terpy)2](BF4)2.

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The xsolid values from the [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 and

[Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 systems are tightly distributed compared to the data points for the [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 system. Based on the spread of xsolid values for each batch (also evident from the standard deviations in Table 14), it appears that the degree of supramolecular selection occurring during co-crystallisation is greatest for the [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 system as the spread for this system is the largest. Since supramolecular selection is rationalised to be dependent on intermolecular interactions between complexes, it II seems that interactions between [M (terpyOH)2](BF4)2 and [Ru(terpy)2](BF4)2 II (M = Fe, Cu) are more favourable than interactions between [Ni(terpyOH)2](BF4)2 and [Ru(terpy)2](BF4)2.

II Statistically, the average [M (terpyOH)2](BF4)2 mole fractions (xsolid) for all of the co-crystallisation experiments were found to be greater than 0.50. In fact, the majority of the co-crystals analysed from all of the systems were found to have II higher concentrations of the [M (terpyOH)2](BF4)2 complex and none of the

[Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals that were measured were found to have concentrations of [Fe(terpyOH)2](BF4)2 less than 0.50. These results suggest that under these crystallising conditions, the two complexes in each of the co-crystallising solutions have different solubilities. Measurements taken from the powder obtained by evaporating the solvent from the mother liquors confirm this, as II higher concentrations of [Ru(terpy)2](BF4)2 relative to [M (terpyOH)2](BF4)2 were found. These are represented by the red data points enclosed in the red box in Figure 40. Measurements taken from crushed single co-crystals found the relative II [M (terpyOH)2](BF4)2 concentration to be on average 0.06 higher than the relative concentration found on the surface. This provides further evidence that the two complexes in each co-crystallising solution have different solubilities thus forming co-crystals with a subtle concentration gradient.

II For these systems, it may be rationalised that [M (terpyOH)2](BF4)2 crystallises first with some of [Ru(terpy)2](BF4)2. As this process continues the solution concentration II of [M (terpyOH)2](BF4)2 slightly decreases relative to [Ru(terpy)2](BF4)2. Therefore, the relative concentrations of the two complexes constantly change during co-crystallisation and as such, the concentration in the co-crystals also changes

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CHAPTER 4 during co-crystal growth. The result is the formation of co-crystals that contain a slight concentration gradient. Therefore, the results presented here suggest that the co-crystallisation process for these systems is influenced by both the difference in the II solubilities of [M (terpyOH)2](BF4)2 and [Ru(terpy)2](BF4)2 and by supramolecular selection.

For systems that involve complexes with similar solubilities such as those that form A B co-crystals with the general formula [M xM 1-x(terpy)2](PF6)2, supramolecular selection is hypothesised to be due to molecular recognition processes, whereby interactions between like complexes are slightly more favoured over interactions between different complexes. This favourability causes one co-crystal to nucleate with a slightly higher proportion of complex A to complex B and vice versa, which then continues as a selection bias during co-crystal growth in favour of the complex in greater proportion. However, for systems that involve complexes with different solubilities, such as those discussed here, the selection bias that occurs during co-crystallisation is likely instigated by the differences in solubility between the II complexes. This reasoning explains the greater proportion of [M (terpyOH)2](BF4)2 that was found in the co-crystals as well as the variation in metal ratios between co-crystals harvested from the same batch.

The difference between complexes in homoleptic experiments such as A B [M xM 1-x(terpy)2](PF6)2 occurs at the metal centre, which is shrouded by ligands and therefore unseen by other complexes in solution. It has been demonstrated that this unseen variation between complexes is being recognised beyond the point of difference giving rise to systems that display supramolecular selection. Unlike the A B [M xM 1-x(terpy)2](PF6)2 homoleptic systems, molecular recognition processes II 2+ 2+ between [M (terpyOH)2] and [Ru(terpy)2] complexes are influenced by differences introduced at the metal centre and 4′-carbon position of the ligand. The differences between the ligands is a variation that is visible to other complexes during co-crystallisation.

Information relating to the structure and phase of pure samples and co-crystals were ascertained using X-ray diffraction characterisation techniques. Figure 41 shows the powder diffraction patterns of freshly prepared pure [Ru(terpy)2](BF4)2 and

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II II [M (terpyOH)2](BF4)2 crystals (M = Fe, Ni, Cu). Patterns simulated from single crystal structures are also shown. Figure 42 - Figure 44 show the powder diffraction II patterns of the various [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals, that were II co-crystallised from solutions containing equimolar ratios of [M (terpyOH)2](BF4)2 II and [Ru(terpy)2](BF4)2 (M = Fe, Ni, Cu). These figures also show the powder patterns obtained from the pure complexes that were present in the co-crystallisation solution and a pattern simulated from SCXRD data collected from the corresponding II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 single co-crystal. The patterns simulated from single crystal data were used as reference patterns to assign Miller indices to the peaks in the corresponding experimentally obtained PXRD patterns. Simulated reference patterns are shown above the experimentally obtained patterns for which they match. The labelled dotted lines emphasise the positions of the prominent peaks that are present in like patterns. Powder patterns and experimental single crystal data were collected at room temperature and 100 K respectively. Refer to Sections 3.2.2 and 3.2.3 for full preparative details.

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II II PXRD: [M (terpyOH)2](BF4)2 (M = Fe, Ni, Cu) and [Ru(terpy)2](BF4)2 200 Simulated from SCXRD 011 101 11-2 020 of [Ni(terpyOH)2](BF4)2 002 (P21) 110 112 122 212

[Cu(terpyOH)2](BF4)2

[Ni(terpyOH)2](BF4)2

1-21 01-1 102 1-10 004 CAPXUN (P1) 113 021 202 100 [Fe(terpyOH)2](BF4)2

003

Counts Counts [Fe(terpyOH)2](BF4)2

312 Simulated from SCXRD of 112 118 [Ru(terpy) ](BF ) 004 204 220 2 4 2 314 (I41/a)

[Ru(terpy)2](BF4)2

5 10 1515 20 25 3030 Position [°2θ (Cu)]

Figure 41: Powder XRD patterns of freshly prepared pure [Ru(terpy)2](BF4)2 and II II [M (terpyOH)2](BF4)2 crystals (M = Fe, Ni, Cu). Miller indices obtained from patterns simulated from SCXRD data were used to index peaks in the experimentally obtained PXRD patterns. The reference [Fe(terpyOH)2](BF4)2 pattern was simulated from a published crystal structure of 271 [Fe(terpyOH)2](BF4)2 deposited in the CSD (reference code CAPXUN).

The [Ru(terpy)2](BF4)2 and [Ni(terpyOH)2](BF4)2 simulated patterns that are shown in Figure 41 were obtained from SCXRD data collected during this research. The crystal structure obtained for [Ni(terpyOH)2](BF4)2 was found to be isomorphous with the published crystal structure for [Cu(terpyOH)2](BF4)2 (not shown, CSD reference code CAPYIC), which was collected at room temperature, albeit with a

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271 slightly smaller unit cell. The [Fe(terpyOH)2](BF4)2 reference trace was simulated from the published crystal structure of [Fe(terpyOH)2](BF4)2 (CSD reference code

271 CAPXUN) that was grown from an MeCN/H2O solution. Refinement data for the published [Cu(terpyOH)2](BF4)2 and [Fe(terpyOH)2](BF4)2 structures (CSD reference codes CAPYIC and CAPXUN) and the experimental [Ni(terpyOH)2](BF4)2 structure collected during this research are provided in Appendix D. The refinement for the [Ru(terpy)2](BF4)2 was problematic due to pseudo-symmetry issues that were not satisfactorily resolved and therefore only the unit cell parameters are presented for this structure in Appendix D. The accompanying CD contains the crystallographic information files (.cif) for these crystal structures.

The data presented in Figure 41 suggest that pure samples of [Ni(terpyOH)2](BF4)2 and [Cu(terpyOH)2](BF4)2 are isomorphous and crystallise in the monoclinic P21 space group. The simulated pattern obtained from SCXRD data collected from a

[Ni(terpyOH)2](BF4)2 single crystal is very similar to the patterns of

[Ni(terpyOH)2](BF4)2 and [Cu(terpyOH)2](BF4)2. The leftward shifts of the peaks in the experimentally obtained powder patterns compared to the same peaks in the pattern simulated from the [Ni(terpyOH)2](BF4)2 structure indicate a slight change in lattice dimensions. This suggests that although the phase remains constant between

100 and 298 K, the lattice dimensions of the [Ni(terpyOH)2](BF4)2 and

[Cu(terpyOH)2](BF4)2 unit cells are slightly larger at room temperature. The experimental [Fe(terpyOH)2](BF4)2 powder pattern correlates well with the pattern simulated from the published structure, which was collected at room temperature and found to belong to the triclinic P1¯ space group (CSD reference code CAPXUN). The peaks at 9.2, 9.8 and 9.9°2θ that are observed in the experimentally obtained

[Fe(terpyOH)2](BF4)2 powder pattern correspond to the [002], [010] and [011] reflections, which are present but very weak in the simulated pattern. The difference in the intensity of these peaks is most likely due to preferred orientation effects as opposed to a phase impurity. The [Ru(terpy)2](BF4)2 powder pattern matches the pattern simulated from the [Ru(terpy)2](BF4)2 tetragonal I41/a structure. The positions of some of the peaks in the experimental [Ru(terpy)2](BF4)2 pattern are slightly to the left of the same peaks in the pattern simulated from the SCXRD data, indicating a slight expansion of the unit cell at room temperature.

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PXRD: [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals from 0.50:0.50 solution (xsolution = 0.50) 102 Simulated from SCXRD of 002 01-3 12000 [Fe(terpyOH) ] [Ru(terpy) ] (BF ) 100 01-1 2 0.60 2 0.40 4 2 (P1) 110 1-21 1-1-1 021 10000 213 113 202

8000

[Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2

6000

Counts Counts Counts [Fe(terpyOH)2](BF4)2 4000

2000

[Ru(terpy)2](BF4)2

0 55 1010 1515 2020 2525 3030 Position [°2θ (Cu)]

Figure 42: Powder XRD patterns of freshly prepared [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals (purple) shown with the diffraction patterns of [Fe(terpyOH)2](BF4)2 (black) and [Ru(terpy)2](BF4)2 (black). A pattern simulated from the SCXRD structure of [Fe(terpyOH)2]0.60[Ru(terpy)2]0.40(BF4)2 (grey) is shown at the very top of the figure and was used to assign Miller indices to the like patterns shown. The peak highlighted in purple at 10.8°2θ is likely the [101] peak that has shifted from underneath the very intense [100] reflection. Although not seen here, the [101] peak occurs at 10.5°2θ in the simulated pattern.

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PXRD: [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals from 0.50:0.50 solution (xsolution = 0.50) 011 Simulated from SCXRD of 12000 101 [Ni(terpyOH) ] [Ru(terpy) ] (BF ) 10-1 2 0.60 2 0.40 4 2 200 (P21) 002 112 210 020 11-2 122 10000 10-4 212

8000

[Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2

6000 Counts Counts [Ni(terpyOH) ](BF ) 4000 2 4 2

2000

[Ru(terpy)2](BF4)2

0 5 1010 1515 2020 2525 3030 Position [°2θ (Cu)]

Figure 43: Powder XRD patterns of freshly prepared [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals (green) shown with the diffraction patterns of [Ni(terpyOH)2](BF4)2 (black) and [Ru(terpy)2](BF4)2 (black). A pattern simulated from the SCXRD structure of [Ni(terpyOH)2]0.60[Ru(terpy)2]0.40(BF4)2 (grey) is shown at the very top of the figure and was used to assign Miller indices to the like patterns shown.

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PXRD: [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals from 0.50:0.50 solution (xsolution = 0.50) 101 011 Simulated from SCXRD of 10-1 [Cu(terpyOH) ] [Ru(terpy) ] (BF ) 12000 002 2 0.50 2 0.50 4 2 10-4 (P21) 112 200 210 122 10000 11-2 020 212

8000

[Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2

6000 Counts Counts [Cu(terpyOH) ](BF ) 4000 2 4 2

2000

[Ru(terpy)2](BF4)2

0 5 1010 1515 2020 2525 3030 Position [°2θ (Cu)]

Figure 44: Powder XRD patterns of freshly prepared [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals (red) shown with the diffraction patterns of [Cu(terpyOH)2](BF4)2 (black) and [Ru(terpy)2](BF4)2 (black). A pattern simulated from the SCXRD structure of [Cu(terpyOH)2]0.50[Ru(terpy)2]0.50(BF4)2 (grey) is shown at the very top of the figure and was used to assign Miller indices to the like patterns shown.

II The single crystal structures of the [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals (MII = Fe, Ni, Cu) were found to be isomorphous with the corresponding II [M (terpyOH)2](BF4)2 complex. The positions of the metal sites are coincident and were modelled as disordered mixtures of MII and Ru (MII = Fe, Ni, Cu) and their relative occupancies were refined (with fixed and equivalent displacement parameters) to 0.63 Fe and 0.37 Ru for [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2, 0.60 Ni and 0.40 Ru for [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 and 0.55 Cu and 0.45 Ru for

[Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2. These values are in agreement to those obtained by SEM-EDX, which showed that co-crystals of this type crystallised with II higher proportions of the [M (terpyOH)2](BF4)2 complex relative to

[Ru(terpy)2](BF4)2. Final refinement cycles for each structure were conducted with the relative occupancies of MII position and the oxygen atoms at the 4′-carbon positions fixed at 0.60 for [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 and

[Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 and 0.50 for

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* [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2. Each unit cell was also found to contain one - - water molecule, one ordered BF4 and one rotationally disordered BF4 counterion. Appendix E summarises the crystal refinement data for these co-crystals. The accompanying CD contains the crystallographic information files (.cif) for these crystal structures.

The powder patterns of the co-crystallised samples that are shown in Figure II 43 and Figure 44 look similar to the [M (terpyOH)2](BF4)2 pattern and the pattern simulated from the SCXRD that are shown within the same figure. The relative peak intensities in the experimentally obtained [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 powder pattern (shown in purple in Figure 42) do not match the relative intensities observed in the [Fe(terpyOH)2](BF4)2 and simulated patterns. This discrepancy is most obvious for the [002] and [01-3] reflections as they are relatively much larger in the purple pattern than in the [Fe(terpyOH)2](BF4)2 or simulated patterns. This is likely caused by preferred orientation effects, which arise when crystallites in a powder are orientated in some ways more often than others. The patterns for the

[Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 and [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 systems (Figure 43 and Figure 44 respectively) suggests that there are minimal preferred orientation effects.

Also there is a peak at 10.8°2θ in the [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 PXRD pattern that is not observed in the [Fe(terpyOH)2](BF4)2 or simulated patterns. This peak could be due to the shift of the [101] reflection from underneath the very intense [100] peak. Although not seen here, the

[Fe(terpyOH)2]0.60[Ru(terpy)2]0.40(BF4)2 simulated pattern contains a peak at 10.5°2θ that is concealed under the [100] reflection. This extra peak could also be due to a phase impurity as it coincides with the [Ru(terpy)2](BF4)2 [112] reflection. All of the other major [Ru(terpy)2](BF4)2 reflections occur at the same position as peaks in the pure [Fe(terpyOH)2](BF4)2 pattern and the pattern simulated from the

[Fe(terpyOH)2]0.60[Ru(terpy)2]0.40(BF4)2 structure. Since no bright red sheet-like

* SEM-EDX data of the same [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystal was obtained upon completion of SCXRD data and suggested xsolid = 0.60 ± 0.02. For each of the SCXRD datasets discussed herein, when the relative occupancies were fixed at Ru 0.40 or 0.50 prior to refinement, only very minimal changes in the refinement residuals were observed. Hence, the final refinement cycles were performed with the relative occupancies fixed at the values stipulated.

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CHAPTER 4 crystals were observed in any of the co-crystallisation batches, a phase impurity is unlikely. None of the other systems show any signs of phase impurities. Overall the II PXRD patterns collected from [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals II strongly suggest that the bulk sample is composed of the [M (terpyOH)2](BF4)2 phase; P1¯ for [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 and P21 for

[Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 and [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2. No significant evidence points to the formation of co-crystals that belong to the tetragonal I41/a [Ru(terpy)2](BF4)2 phase.

II II Experiments where [M (terpyOH)2](BF4)2 (M = Fe, Ni, Cu) were co-crystallised with [Ru(terpy)2](BF4)2 in 0.05:0.95 ratios (xsolid = 0.05) were conducted to test II 2+ whether [M (terpyOH)2] complexes could adopt the tetragonal I41/a

[Ru(terpy)2](BF4)2 phase. Representative SEM-EDX statistical data for these systems are summarised in Table 15 in the same manner as those for analogous 0.50:0.50 experiments.

Figure 45 is a colour-coded graphical representation of the same EDX information summarised in Table 15. The horizontal axis shows the different combinations of co-crystallised metal complexes and hence the metal ratios of interest and are labelled from left to right as Fe:Ru, Co:Ru, Ni:Ru and Cu:Ru. In addition, the measurements from each batch are labelled with the general formula i.e. measurements from the Ni:Ru batch are labelled II [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2. The y axis is labelled M xsolid, thus for the

Ni:Ru system, this refers to the x variable in the [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 formula, and is the atomic fraction of Ni detected in the solid by SEM-EDX. Note that the y axis has been expanded showing a range of 0.00-0.20 so that data points can be viewed with minimal overlap. It is important to note that data points of the same colour/shape represent measurements taken from any particular co-crystal within a co-crystallisation batch. So for example, the data points outlined by the blue box, are from a different co-crystal to those outlined by the orange box, but both sets of measurements were from co-crystals grown from the same solution.

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Table 15: Statistical summary of xsolid values obtained from EDX data for experiments resulting in II co-crystals with the general formula [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 that were formed from II solutions containing 5% [M (terpyOH)2](BF4)2. The sample mean (xˉ), standard deviation (s), the II minimum, maximum and range of M xsolid values are shown along with the co-crystal formula. The xsolid data correspond to the element in bold.

Co-crystallising systems xˉ(xsolid) s(xsolid) Minimum Maximum Range

[Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 0.09 0.03 0.03 0.12 0.09

[Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 0.07 0.04 0.03 0.12 0.09

[Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 0.08 0.04 0.05 0.17 0.12

II EDX GRAPHICAL SUMMARY: [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 from 0.05:0.95 solutions 0.200.20

[Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2

0.150.15

[Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2

solid solid solid solid

x x x

x 0.100.10

II II II II

M M M M

[Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2

0.050.05

0.000.00 0 Fe:Ru0.1 Ni:Ru0.2 Cu:Ru0.3 0.4 Co-crystallisation experiment

Figure 45: Colour-coded plot of EDX results of co-crystals of the general formula II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 that were grown from solutions containing 5% II [M (terpyOH)2](BF4)2. The horizontal axis shows the metal ratios of interest and are labelled from left II to right as Fe:Ru, Ni:Ru and Cu:Ru. The y axis is labelled M xsolid, and corresponds to the atomic fraction of MII detected in the solid by SEM-EDX.

The mother liquors at the time the co-crystals were harvested were still intensely red indicating that a significant proportion of [Ru(terpy)2](BF4)2 remained in solution. SEM-EDX of the solid residue obtained from evaporating the mother liquors II indicated that negligible amounts of the [M (terpyOH)2](BF4)2 remained in solution.

It may appear that repeat measurements taken from a single co-crystal within a batch deviate significantly from one another; however, upon closer inspection, this observation is simply a visual illusion due to the small amounts of MII detected in the

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CHAPTER 4 solid.* As with the analogous 0.50:0.50 experiments, the SEM-EDX data for these experiments show clustered data points for measurements taken from the same co-crystal (± 0.03). These results show that allowing for instrumental error, the ratio of the two complexes in each single co-crystal varies very little over the areas measured.

Differences between measurements obtained from crushed co-crystals and those made on the co-crystal surface were not significant (differences of 0.01-0.02).

However, the average xsolid values from different co-crystals grown from the same batch were observed to differ significantly; between 0.05-0.10 depending on the co-crystallising system, such that xsolid single co-crystal 1 ≠ xsolid single co-crystal 2. As observed for the 0.50:0.50 experiments, these data also indicate that II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals grown from a solution containing II II only 5% [M (terpyOH)2](BF4)2 can have a range of [M (terpyOH)2](BF4)2 concentrations relative to [Ru(terpy)2](BF4)2. Overall, the data suggest that even at II [M (terpyOH)2](BF4)2 initial solution concentrations of 5% relative to

[Ru(terpy)2](BF4)2, some degree of supramolecular selection occurs during co-crystallisation.

The structures of the resulting co-crystals were inferred through the collection of II PXRD patterns. The [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 powder patterns (MII = Fe, Cu) for co-crystals grown from solutions containing 5% II [M (terpyOH)2](BF4)2 are shown in Figure 46 with the pattern of pure

[Ru(terpy)2](BF4)2. Figure 47 shows the powder patterns of

[Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2, [Ni(terpyOH)2](BF4)2 and [Ru(terpy)2](BF4)2.

* Absolute instrumental error remains the same, however, relative instrumental error is larger due to II smaller M xsolid values that are obtained. 116

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II PXRD: [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals II II (M = Fe, Cu) from 0.05:0.95 solution (M xsolution = 0.05) 9000

8000 [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 7000

6000

5000 [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 4000

3000

2000 Counts

1000 [Ru(terpy)2](BF4)2

0 55 1010 1515 2020 2525 3030 Position [ 2θ (Cu)]

Figure 46: Powder XRD patterns of freshly prepared [Fe(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (purple) [Cu(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals (red) that were grown from solutions containing 5% II II [M (terpyOH)2](BF4)2 (M = Fe, Cu). The [Ru(terpy)2](BF4)2 diffraction pattern is also shown (black). The dotted lines emphasise the similarities between the patterns shown.

PXRD: [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals from II 0.05:0.95 solution (M xsolution = 0.05) 9000

8000 [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 7000

6000

5000

4000 [Ni(terpyOH)2](BF4)2

3000

2000Counts

1000 [Ru(terpy)2](BF4)2

0 55 1010 1515 2020 2525 3030 Position [ 2θ (Cu)]

Figure 47: Powder XRD pattern of freshly prepared [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (green) co-crystals that were grown from a solution containing 5% [Ni(terpyOH)2](BF4)2. Diffraction patterns of [Ni(terpyOH)2](BF4)2 and [Ru(terpy)2](BF4)2 are also shown (black). The dotted lines emphasise the similarities between the patterns shown. The peaks highlighted by shaded area in the green pattern have different relative intensities to the peaks in the [Ni(terpyOH)2](BF4)2 pattern. This is likely due to preferred orientation effects.

Interpretation of the diffraction patterns shown in Figure 46 suggests that II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals grown from solutions containing II II 5% [M (terpyOH)2](BF4)2 (M = Fe, Cu) adopted the tetragonal I41/a II [Ru(terpy)2](BF4)2 phase. There is no evidence of the [M (terpyOH)2](BF4)2 phase in these patterns. The [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 pattern shown in Figure 47

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shares many similarities with the [Ni(terpyOH)2](BF4)2 shown. The peaks highlighted by shaded area in the green pattern have different relative intensities to the peaks in the [Ni(terpyOH)2](BF4)2 pattern. The relative intensities of the peaks in the low angle region (8-11°2θ) are also different in the co-crystal pattern to those in the [Ni(terpyOH)2](BF4)2 pattern. This distortion in the relative peak intensities is most likely due to preferred orientation effects. Overall, the patterns shown in Figure

47 suggest that [Ni(terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals grown from a solution containing 5% [Ni(terpyOH)2](BF4)2 adopt the monoclinic P21

[Ni(terpyOH)2](BF4)2 phase.

II 4.3.3 Co-crystallisation experiments involving [M (terpyPh)2](PF6)2,

[Ni(phen)3](PF6)2 and [Ni(bipy)3](PF6)2

The following experiments were designed to test the effects of large differences between complexes, which are chemically and structurally different on the II 2+ co-crystallisation process. The main differences between [M (terpy)2] and 2+ [Ni(L)3] complexes (L = phen, bipy) is that the former has S4 point symmetry, while the latter has D3 point symmetry. Regardless of the structural differences between the all of the complexes involved in these experiments, each metal complex is of a similar size and forms structures by engaging in some combination of OFF 2+ 2+ and/or EF interactions. More specifically cation pairs of [Ni(phen)3] , [Ru(terpy)2] 2+ and [Ru(terpyPh)2] all interact through one OFF and two EF interactions (phen and 2+ terpy motifs respectively). Cation pairs of [Ni(bipy)3] interact through a set of six EF interactions. Therefore, in theory it is possible to form co-crystals of the general II formula [M (terpyPh)2]x[Ru(terpy)2]1-x(PF6)2, [Ni(L)3]x[Ru(terpy)2]1-x(PF6)2 or

[Ni(L)3]x[Ru(terpyPh)2]1-x(PF6)2. Previous co-crystallisation experiments conducted A B A B by our group, of the type [M (bipy)3]x[M (phen)3]1-x(PF6)2 (M , M = Ni, Ru) demonstrated that it is possible to combine two different motifs to form single co-crystals containing both complexes.261,306

Several different ligand co-crystallisation experiments involving II [M (terpyPh)2](PF6)2, [Ni(phen)3](PF6)2 and [Ni(bipy)3](PF6)2 were conducted. II II Complexes with the formula [M (terpyPh)2](PF6)2 (M = Fe, Ni, Cu) were co-crystallised with [Ru(terpy)2](PF6)2 with the aim of forming co-crystals with the

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II formula [M (terpyPh)2]x[Ru(terpy)2]1-x(PF6)2. The aim of experiments where

[Ni(phen)3](PF6)2 or [Ni(bipy)3](PF6)2 were co-crystallised with either

[Ru(terpy)2](PF6)2 or [Ru(terpyPh)2](PF6)2 was to form co-crystals with the general formula [Ni(L)3]x[Ru(terpy)2]1-x(PF6)2 and [Ni(L)3]x[Ru(terpyPh)2]1-x(PF6)2 (L = phen, bipy).

Crystallisations were conducted using the slow evaporation method (1:1

MeCN:H2O). Table 16 summarises the co-crystallisation experiments. Each batch combination was conducted twice to test reproducibility. Due to the results obtained from the first two replicates, the vials in the third set of experiments were stoppered after only partial co-crystallisation (after ca. one day). This last set of experiments was conducted to test for any solubility differences between the complexes. Ten co-crystals from each batch were analysed by SEM-EDX. This table summarises 21 co-crystallisation experiments. For exact preparative experimental details, refer to Section 3.3.5.1.

Table 16: Summary of co-crystallisation experiments showing all metal complexes involved, their colours and relative solution concentrations.

Complex A (colour) Complex B (red) Fraction of A in solution (xsolution)

[Fe(terpyPh)2](PF6)2 (purple) [Ru(terpy)2](PF6)2 0.50

[Ni(terpyPh)2](PF6)2 (tan) [Ru(terpy)2](PF6)2 0.50

[Cu(terpyPh)2](PF6)2 (blue) [Ru(terpy)2](PF6)2 0.20, 0.50 and 0.80

[Ni(phen)3](PF6)2 (pink) [Ru(terpy)2](PF6)2

[Ni(bipy)3](PF6)2 (pink) [Ru(terpy)2](PF6)2 0.80 [Ni(phen)3](PF6)2 (pink) [Ru(terpyPh)2](PF6)2

[Ni(bipy)3](PF6)2 (pink) [Ru(terpyPh)2](PF6)2

Repeated co-crystallisation experiments resulted in samples containing only pure crystals of both complexes. The result was initially verified under an optical microscope using the different colours and crystal habits of the pure complexes as indicators of co-crystallisation. In each batch, two distinct types of crystals were observed, each type of the same colour and habit of the crystals of the pure starting materials. SEM-EDX measurements conducted on both types of crystal in each batch confirmed that no co-crystallisation had occurred. SEM-EDX measurements conducted on the crystals that formed from experiments that were allowed to only

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CHAPTER 4 partially co-crystallise also formed crystals of both types of complex. Furthermore, analysis of the residue obtained by evaporating the mother liquors indicated the presence of both complexes in solution. These findings suggest that the cause of these results is likely due to molecular recognition leading to extreme supramolecular selection as opposed to solubility differences between the complexes in solution i.e. complex A did not completely crystallise out before complex B (or vice versa). Therefore, it appears that the supramolecular interactions of the two complexes in each co-crystallisation experiment shown in Table 16 are too different to allow the complexes to co-crystallise.

4.4 Chapter summary and conclusions

It was possible to exploit the 2D terpy embrace motif to synthesise four II II [M xRu1-x(terpy)2](PF6)2 (M = Fe, Co, Ni, Cu) and five II II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (M = Fe, Ni, Cu) novel co-crystals. Co-crystals were characterised using XRD and SEM-EDX, the former to examine phase and structure and the latter to quantify the amount of each metal complex present in single co-crystals. XRD data for co-crystals from both systems suggested the presence of a single phase and in the case of co-crystals grown from equimolar - - solutions, indicated the absence of the [Ru(terpy)2]X2 (X = BF4 , PF6 ) phase. This suggested that the [Ru(terpy)2]X2 structure is less robust as it was unable to II II accommodate [M (terpy)2](PF6)2 or [M (terpyOH)2](BF4)2 complexes at xsolution values of 0.50. The [Ru(terpy)2](BF4)2 phase was exclusively adopted in co-crystals II II of [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (M = Fe, Cu) when the xsolution of II [M (terpyOH)2](BF4)2 was 0.05. SEM-EDX results for both types of systems indicated that co-crystals grown from the same solution had a range of concentrations such that xsolid single crystal 1 ≠ xsolid single crystal 2 and thus suggested that complexes exhibited supramolecular selection.

Only crystals of pure complexes were obtained for experiments where

[Co(terpyO)(terpyOH)](BF4)2 was co-crystallised with [Ru(terpy)2](BF4)2, II II [M (terpyPh)2](PF6)2 (M = Fe, Ni, Cu) were co-crystallised with [Ru(terpy)2](PF6)2 and where [Ni(L)3](PF6)2 (L = phen, bipy) were co-crystallised with

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[Ru(terpy)2](PF6)2 or [Ru(terpyPh)2](PF6)2. The absence of any co-crystals suggested that despite the apparent similarities between the complexes being co-crystallised these combinations surpassed the limit for which molecular recognition processes can be confused into co-crystallising different molecules into the same crystalline lattice.

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CHAPTER 5: Co-crystallisation systems incorporating III 3- [M (ox)3] to form framework materials

5.1 Background and introduction

5.1.1 The oxalato ligand (ox) and coordination frameworks containing III 3- [M (ox)3] complexes as building-blocks

The oxalate dianion, for which the chemical structure is shown in Figure 48, is planar, achiral and resonance-stabilised. It usually binds to metals as a bidentate ligand forming a five-membered chelate ring. These properties are all similar to those of polypyridyl ligands such as 2,2′-bipyridine and 1,10-phenanthroline, which are also shown in Figure 48.56

2- 2- 2- O O O O O O

N N N N O O N N N N N N N N O O O O (a) (b) (c) Figure 48: The structures of oxalate (a), 2,2′-bipyridine (b) and 1,10-phenanthroline (c).

Unlike the polypyridyl ligands shown in Figure 48 (b) and (c), which are neutral N-donor ligands, oxalate is a dianionic O-donor ligand. In addition, oxalate is capable of forming bridged polynuclear complexes, potentially coordinating through all four of its oxygen atoms, and as such is a versatile ligand for building metal-organic framework structures.31,247,310,311 These polymeric structures often have π-electron delocalisation along the entire metal-organic framework. As a result, oxalate is an excellent mediator of electronic communication between metal centres of neighbouring coordination spheres leading to interesting electronic and magnetic properties such as long range magnetic ordering. Due to these attractive attributes oxalate is an extensively used ligand in the field of molecular magnetism.124,186,248,312-316

III 3- Tris-oxalato metalates with the general formula [M (ox)3] are widely-used oxalate containing moieties that serve as building-blocks in the formation of metal-organic III 3- coordination frameworks. Like all tris-bidentate metal complexes, [M (ox)3] complexes adopt a propeller-like structure that exists as either Δ or Λ optical isomers

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and thus possesses chiral octahedral D3 symmetry. A schematic of both enantiomers is shown in Figure 49.

z- mirror z- Δ-[M(ox)3] Λ-[M(ox)3] z- z- Figure 49: Schematic views showing the propeller-like geometry of Δ-[M(ox)3] and Λ-[M(ox)3] enantiomers.

Many synthetic and naturally occurring metal-organic framework structures III 3- containing [M (ox)3] are reported in the literature. With regards to their chemical III 3- formula, the simplest [M (ox)3] containing coordination frameworks are those with III + the general formula A3[M (ox)3]·xH2O, where A is a univalent cation such as K and MIII is a trivalent transition metal. The naturally occurring mineral Minguzzite III + + + (K3[Fe(ox)3]·3H2O) and synthetic A3[M (ox)3]·xH2O analogues (A = Li , Na , K , + + III Rb , NH4 ; M = Al, V, Cr, Mn, Fe) are known to form isomorphous 3D

317-329 coordination frameworks that crystallise in the space group P21/c. These and III 3- other [M (ox)3] complexes are often used as precursors in the formation of 2D248,316,325,330-337 and 3D31,290,315,338-342 homo- and hetero-bimetallic coordination frameworks that are capable of behaving as multifunctional magnets.

The discrimination between the formation of either the 2D or 3D homo- and hetero-bimetallic coordination frameworks is known to depend on the choice of the templating cation. The cation has also been found to determine the overall chirality

313,314,338,343 + of the structure. Bulky organic monocations of the general formula [XR4] (X = N, P; R = n-alkyl, Ph) are known to initiate the polymerisation of 2D layered II III structures with the formula [XR4][M M (ox)3]. These structures form a 6-gon 3-connected (6,3) framework consisting of 2D anionic honeycomb layers of II III - II III the general formula {[M M (ox)3] }n (M = V, Mn, Fe, Co, Ni, Cu, Zn; M = V, Cr, Mn, Fe, Ru, Rh) that are interleaved by the templating organic cations. Within each anionic layer all of the MIII sites have the same chirality (Δ or Λ) while all of the MII sites adopt the opposite configuration resulting in a heterochiral

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CHAPTER 5 arrangement.344,345 A schematic of this arrangement is shown in Figure 50. These kinds of frameworks usually belong to the achiral R3c space group whereby each unit cell consists of six anionic and six cationic layers. Alternate anionic layers contain MIII units of opposite configuration leading to optically inactive racemic crystals. The size of the organic cation is known to determine the interlayer separation between anionic layers.310 Several compounds of this type and diluted II II III structures such as NBu4[Fe xMn 1-xCr (ox)3] are reported in the literature, of which many have been shown to exhibit interesting ferro- ferri- and weak antiferromagnetic long range ordering. 187,248,316,325,330-338

Δ Λ Figure 50: A schematic representation of the heterochiral arrangement of neighbouring metal centres leading to the formation of a 2D (6,3) hexagonal anionic framework.346

Interestingly, the use of a metallic mono-cation such as Na+ together with a metallic di-cation such as Mg2+ yields coordination frameworks of the formula II I III M [M M (ox)3]·xH2O that form very similar heterochiral 2D layered structures. In these structures the 2D anionic honeycomb layers, which have the general formula I III 2- {[M M (ox)3] }n are interleaved by hexaaqua metal complex cations such as 2+ [Mg(H2O)6] . Coordination frameworks of this type have been studied for their interesting photophysical and magnetic properties, especially in Cr3+-doped

175-181,240-244,347-352 Mg[NaAl(ox)3]·xH2O structures.

The formation of chiral 3D homo- and hetero-metallic helical anionic frameworks of II 2- I III 2- II III - the general formula {[M 2(ox)3] }n ,{[M M (ox)3] }n, and {[M M (ox)3] }n are known to be templated by the propeller-like structure, and hence the chiral octahedral

D3 symmetry of tris-diimine transition metal complexes of the general formula 2+/3+ + II III [M(L)3] or [M(L)2L′] (M = M , M and L = 1,10-phenanthroline, 2,2′-bipyridine, L′ = 8-hydroxyquinoleate, 2-phenylpyridine-H+). These cations

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CHAPTER 5 template the formation of 10-gon 3-connected (10,3) anionic frameworks where the z- metal ions are located at the ten vertices of a decagon and the [M(ox)3] moieties behave as 3-point connecting nodes. The result is the formation of three sets of interconnected helices of identical helicity where all of the metal sites in the framework have the same chirality (all Δ or all Λ).344-346 A schematic of this arrangement is shown in Figure 51.

M2(Δ)

M1(Δ)

Δ Δ

Figure 51: A schematic representation of the homochiral arrangement of neighbouring metal centres I II II III with Δ chirality (M1 = M or M ; M2 = M or M ) leading to the formation of a 3D (10,3) helical anionic framework. For clarity purposes only one helix is shown.310,346

The metal complex cations are situated within cavities created by the interconnected anionic helices. The metal sites of the cationic metal complex guests have the same chirality as the metal sites of the anionic framework resulting in a homochiral structure such that each single crystal is enantiomerically pure. A schematic of this host-guest arrangement between the anionic framework and the metal complex cations is shown in Figure 52. The cavities are also flexible enough to accommodate - - - - small monoanions (X ) such as ClO4 , BF4 or PF6 . These ions are necessary for II II III III I III structures such as [M (L)3][M M (ox)3]X, [M (L)3][M M (ox)3]X and III II [M (L)3][M 2(ox)3]X where the combination of the anionic framework and templating cation result in a net positive charge. These 3D coordination metal-organic frameworks and those without the small monoanions (X-) usually belong to enantiomorphic cubic space groups such as P4332 and P4132 for II 2- homometallic structures containing {[M 2(ox)3] }n moieties and P213 for I III 2- II III - heterometallic structures containing {[M M (ox)3] }n, or {[M M (ox)3] }n units.63,314,344,345 Several 3D coordination framework compounds of these types are reported in the literature, of which many have been shown to exhibit properties such as molecular magnetism and photophysics. 290,310,315,337-342,353-356

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2- Figure 52: [100] projection of the anionic Δ-{[LiCr(ox)3] }n host framework (left) and the cationic 2+ 310 Δ-[Ru(bipy)3] guests (right) for the Δ-[Ru(bipy)3][LiCr(ox)3] structure reported by Andrés et al.

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5.2 Results and discussion

Thus far, co-crystallisation experiments discussed within this thesis have only involved systems that yield single co-crystals that form structures with discrete molecules. The term molecular structure describes crystal structures that exhibit non-polymeric arrays. For these systems, metal complexes in the solid state generally only interact through weak intermolecular forces to form supramolecular motifs. Consequently, co-crystals of this type are usually soluble in common solvents and once dissolved, dissociate to give the original metal complex ions. Co-crystals with A B A B the formula [M xM 1-x(L)n]X2 (M , M = divalent metal cations; x = molar fraction of MA relative to MB in the crystalline state (as determined by SEM-EDX); L = phen, bipy, terpy, terpyOH, terpyPh) are examples of molecular systems that have been studied.261,306,307

Overall, it was found that the solid state compositions (i.e. the metal complex ratios as determined by SEM-EDX) single co-crystals with the general formula A B [M xM 1-x(L)n]X2 varied from the metal complex ratios in solution i.e. xsolid ≠ xsolution. In addition, it was found that for these systems, co-crystals grown from the same solution ranged in composition i.e. xsolid single co-crystal 1 ≠ xsolid single co-crystal 2. These results were attributed to a mechanism of supramolecular selection, which is thought to be influenced by molecular recognition processes between the metal complexes being co-crystallised during co-crystal growth. In the systems investigated thus far, the supramolecular motifs have been mostly influenced by π-interactions between ligands of neighbouring complexes. It should be noted, that of all the molecular A B co-crystallisation systems investigated so far, only [M xM 1-x(phen)3]X2 systems were shown not to display supramolecular selection i.e. xsolid = xsolution and xsolid single co-crystal 1 = xsolid single co-crystal 2, but further experiments have demonstrated that this system is the exception rather than the rule. A detailed explanation of this hypothesis can be found in Section 1.6.3.

For all of the homoleptic experiments conducted thus far that produced molecular co-crystals, the geometric differences between the metal complexes being co-crystallised in any one batch were almost negligible. For example, parameters II 2+ II such as bite and twist angles for [M (bipy)3] (M is a first or second row transition

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CHAPTER 5 metal such Ni2+ or Ru2+) vary by the smallest margins. It therefore very interesting A B z that the disparity between the metal centres in simple binary [M xM 1-x(L)n] systems is being recognised beyond the point of difference, as intermolecular interactions occur between the ligands of neighbouring coordinating spheres and not the metals.

Of all of the ligands used in the co-crystallisation experiments discussed thus far, oxalate is the smallest at about half the size of 2,2′-bipyridine. The resulting III 3- II 2+ [M (ox)3] complexes are therefore also smaller than [M (bipy)3] . Ligand size is thought to be a contributing factor influencing the degree of supramolecular selection during co-crystallisation given that a greater relative structural change is imparted when one metal centre is substituted for another. Previous results obtained from simple binary homoleptic co-crystallisation experiments conducted by the candidate indicated that complexes with smaller ligands exhibited greater supramolecular selection: the metal centre accounted for a larger proportion of the metal complex. For example, as introduced in Section 1.6.3, co-crystallisation experiments which A B involved 2,2′-bipyridine to form [M xM 1-x(bipy)3](PF6)2 co-crystals exhibited supramolecular selection while those that involved the larger but very similar

A B 35 1,10-phenanthroline ligand to form [M xM 1-x(phen)3](PF6)2 co-crystals did not.

III 3- The oxalato ligand and subsequently the [M (ox)3] complexes are negatively charged; so far only cationic complexes have been the focus of co-crystallisation experiments. Furthermore, metal centres of neighbouring coordinate spheres in III 3- [M (ox)3] containing frameworks are linked through metal-oxygen bonds (M-O) due to the bridging capability of the ligand. These recurring M-O bonds are stronger (50-200 kJmol-1) than the π interactions (0-50 kJmol-1) found in the molecular

A B 57 systems such as [M xM 1-x(bipy)3](PF6)2. These factors are known to enhance the electronic communication between the metal centres and may enhance the effects of supramolecular selection through molecular recognition processes during co-crystallisation.

Throughout this research, 3D co-crystalline metal-organic frameworks incorporating III 3- [M (ox)3] complexes were prepared to examine the effects (if any) of bridging neighbouring coordinating spheres on supramolecular selection. Section 5.2.1 III 3- III discusses the co-crystallisation of two different [M (ox)3] metal complexes (M =

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Cr, Mn, Fe, Ru, Rh) in the presence of K+ to form co-crystals of the general formula A B K3[M xM 1-x(ox)3]·xH2O. The results pertaining to epitaxial crystallisation experiments involving the immersion of single crystal seeds of the formula III III III [M (ox)3]·2.5H2O (M = Cr, Fe) into saturated solutions of K3[M (ox)3](aq/EtOH) (MIII = Cr, Fe or a 1:1 mixture) are also presented in this section. Section 5.2.2 III 3- III II 2+ II discusses the co-crystallisation of [M (ox)3] (M = Cr, Fe) with [M (L)3] (M = Ni, Ru; L = bipy, phen) in the presence of Na+ to form co-crystals of the general A B III II A B formula [M xM 1-x(L)3][NaM (ox)3] and [M (L)3][NaM xM 1-x(ox)3].

A B 5.2.1 Co-ordination frameworks of the type K3[M xM 1-x(ox)3]

As mentioned throughout the introductory section to this chapter, the oxalato ligand is a good mediator of long range magnetic order (ferro-, ferri- and antiferromagnetism) between metal centres in polymeric structures. In simple III 3- structures involving the [M (ox)3] subunit, magnetic behaviour is largely dependent on the nature of the transition metal ion and the resulting crystal structure.289,290,314,343,354,357 When recrystallised using the same method, crystals of the III III formula K3[M (ox)3]·3H2O (M = Cr, Mn, Fe) are known to be isomorphous and III III belong to the P21/c space group, while K3[M (ox)3]·4.5H2O (M = Ru, Rh) are isomorphous, forming in the P1¯ space group.318-327,358,359 The PXRD patterns of the pure complexes synthesised during this work are shown in Figure 53. This plot is colour-coded so that each experimental pattern is paired with a matching pattern simulated from literature SCXRD data. The formulae for the experimental patterns (where known) were elucidated from microanalysis data. As expected the patterns III III for K3[M (ox)3]·3H2O (M = Cr, Mn, Fe) are isomorphous belonging to the P21/c space group, while the K3[Ru(ox)3]·xH2O pattern is observed to correlate well to the simulated pattern from the P1¯ structure shown. The experimental pattern for

K3[Rh(ox)3]·2H2O did not match any of the K3[Rh(ox)3] literature patterns nor any of the patterns simulated for K3[Ru(ox)3] but did correlate well with a pattern simulated

360 from data for K3[Co(ox)3]·2H2O (C2/c, CSD reference code DAZVUV).

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III PXRD: K3[M (ox)3]·xH2O pure complexes DAZVUV (C2/c)

K3[Co(ox)3]·2H2O

K3[Rh(ox)3]·2H2O

DUKNOM (P1)

K3[Ru(ox)3]·4.5H2O

K3[Ru(ox)3]·xH2O

GEXQOP (P21/c) K3[Fe(ox)3]·3H2O

K3[Fe(ox)3]·2.5H2O Counts ZZZCCG (P21/c) K3[Mn(ox)3]·3H2O

K3[Mn(ox)3]·xH2O

CROXKH (P21/c) K3[Cr(ox)3]·3H2O

K3[Cr(ox)3]·2.5H2O

55 1010 1515 2020 2525 30 Position [ 2θ (Co)]

III III Figure 53: PXRD patterns of pure and recrystallised K3[M (ox)3]·xH2O (M = Cr, Mn, Fe, Ru, Rh). The plot is colour-coded so that each experimental pattern is shown paired with a pattern simulated from single crystal data found in the CSD database. The CSD reference codes, the space groups and formulae are shown for each simulated pattern.

Several co-crystallisation experiments were conducted by co-crystallising two III different K3[M (ox)3] complexes with the aim of forming single co-crystals of the A B A B formula K3[M xM 1-x(ox)3]·xH2O (M , M = Cr, Mn, Fe, Ru, Rh; 0 < x < 1). For A A experiments involving K3[M (ox)3] (M = Cr, Fe, Ru) fractions in solution (xsolution) ranged from 0.10-0.90. Experiments involving the manganese or rhodium complexes were initially tested at xsolution = 0.50. Experiments where non-isomorphous

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CHAPTER 5 complexes were co-crystallised were of particular interest due to the potential to tune the co-crystalline phase based on the initial xsolution value i.e. observe if and at what A concentration of K3[M (ox)3] one phase is preferred over the other. Also, III III experiments where K3[M (ox)3] (M = first row transition metal) were III III co-crystallised with K3[M (ox)3] (M = second row transition metal) were highly desirable due to the difference in the electron densities about the metal ion. Electron density differences are necessary to differentiate between metal ions in SCXRD and also enhance the difference in the visible contrast observed in backscattered SEM images. Although not a primary objective, it was also hoped that sensitive III K3[M (ox)3] complexes such as K3[Fe(ox)3] could be stabilised through III co-crystallisation with stable K3[M (ox)3] complexes such as K3[Cr(ox)3]. Co-crystallisations were conducted in the dark using the vapour diffusion method of 3 EtOH into H2O (1 cm of H2O for 20 mg of total solid). For exact preperative experimental details, refer to Section 3.3.5.2.

Table 17 summarises the various binary co-crystallisation experiments that were conducted and outlines the metal complexes involved, their stability (as indicated at the foot of the table), the relative fraction of each complex in solution (xsolution) and the results with respect to crystal stability and quality of the resulting solid material. Each co-crystallisation batch was repeated at least three times. For example, the experiment summarised in the second row describes five individual co-crystallisations, each repeated at least three times giving a minimum number of 15 co-crystallisation batches. This table summarises 60 co-crystallisation experiments.

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Table 17: Summary of co-crystallisation experiments showing all metal complexes involved, their relative solution concentrations and whether or not single crystals resulted. The notes at the foot of the table outline the nature of the instability of the pure complexes. Fraction of Complex A Complex B A in solution Stable Single crystals

(xsolution) * K3[Cr(ox)3]·2.5H2O K3[Mn(ox)3]·xH2O 0.50 No --- 0.10-0.90 † K3[Cr(ox)3]·2.5H2O K3[Fe(ox)3]·2.5H2O Yes Yes in 0.20 increments 0.10-0.90 ‡ § K3[Cr(ox)3]·2.5H2O K3[Ru(ox)3]·xH2O No No in 0.20 increments § K3[Cr(ox)3]·2.5H2O K3[Rh(ox)3]·2H2O 0.50 Yes No * † ‡ K3[Mn(ox)3]·xH2O K3[Fe(ox)3]·2.5H2O 0.50 No --- * ‡ K3[Mn(ox)3]·xH2O K3[Ru(ox)3]·xH2O 0.50 No --- 0.10-0.90 † ‡ § K3[Fe(ox)3]·2.5H2O K3[Ru(ox)3]·xH2O No No in 0.20 increments † § K3[Fe(ox)3]·2.5H2O K3[Rh(ox)3]·2H2O 0.50 Yes No *Solid and solution highly photosensitive and thermosensitive. †Highly photosensitive solution state, moderately photosensitive solid state. ‡Solid and solution highly photosensitive and air sensitive. §Some microcrystalline material or complex crystalline aggregates were obtained ---Only amorphous material was obtained

All of the experiments involving K3[Mn(ox)3] resulted in a chalky white amorphous solid material, indicating the reduction of Mn3+ to Mn2+. Some crystalline material was observed to form from combinations with K3[Ru(ox)3] but a large proportion of the solid material that resulted was black and tarry. Initial concentrations of more than 0.30 of K3[Ru(ox)3] gave very little or no crystalline material after the three 3- days of co-crystallisation. Although materials containing [Mn(ox)3] display very interesting magnetic and electronic properties,290,316,361 it was excluded from any further co-crystallisation experiments due to its high photosensitivity and rapid 3+ decomposition. Co-crystals with K3[Ru(ox)3]·xH2O were desirable because Ru is a very heavy atom that is easily distinguishable in SCXRD from first row transition metal complexes. Co-crystallisation experiments with the air- and photo-sensitive

K3[Ru(ox)3]·xH2O were also excluded from further co-crystallisations due to its apparent decomposition during these experiments.

Unlike K3[Ru(ox)3], K3[Rh(ox)3] is stable as both a solid and in solution. It also III III crystallises in a different space group to K3[M (ox)3] (M = Cr, Fe) and contains a second row transition metal, all of which are attributes that are highly desirable for

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CHAPTER 5 these experiments. However, the co-crystallisations were not reproducible with respect to the quality of the crystals that resulted. Of the solid material that formed from each batch, only a select few crystals had surfaces suitable for measurement by SEM-EDX. An example of the various crystal habits and crystal aggregation that resulted is shown in Figure 54, which is an SEM image of co-crystals formed from an equimolar solution of K3[Fe(ox)3] and K3[Rh(ox)3]. Measurements of the flat plate-like crystals showed highly variable fractions of iron over different areas on the same co-crystals with values ranging from 0.12-0.85. The iron content in the acicular-like cluster was lower than the initial solution concentration and ranged from 0.16-0.34 from different areas on the same cluster. Based on the crystal aggregation and differences in crystal habit, systems involving K3[Rh(ox)3] were deemed unsuitable for these studies and as such combinations involving K3[Rh(ox)3] were abandoned.

Figure 54: SEM secondary electron image showing crystal aggregation and the various crystal habits resulting from the equimolar co-crystallisation between K3[Fe(ox)3] and K3[Rh(ox)3]. EDX analysis of the plate like crystals gave an iron fraction anywhere between 0.12-0.85. The acicular like cluster (top right) was found to contain an iron fraction ca. 0.25.

Of the experiments listed in Table 17, only those where K3[Cr(ox)3] was co-crystallised with K3[Fe(ox)3] resulted in high quality single crystals. Co-crystals grown from every batch were blue and formed with a thin rhombohedral prism habit.

Experiments with higher concentrations of K3[Cr(ox)3]·2.5H2O yielded crystals of a darker hue. No green crystals were observed. As expected, the powder XRD patterns of the co-crystals grown from solutions containing various relative fractions of

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K3[Cr(ox)3]·2.5H2O to K3[Fe(ox)3]·2.5H2O were found to be isomorphous, belonging to the same phase as K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O. The PXRD patterns of the co-crystals resulting from co-crystallisations, where

K3[Cr(ox)3]·2.5H2O xsolution values were 0.10, 0.50 and 0.90, can be found in

Appendix C. None of the patterns showed any evidence of K3[Fe(ox)3]·2.5H2O II decomposition, as none of the peaks attributed to Humboldtine ([Fe (ox)2]·2H2O), potassium oxalate or oxalic acid, which are all known products from the

362,363 photodecomposition of K3[Fe(ox)3]·2.5H2O were observed in any of the patterns. All of the patterns appeared to indicate the formation of single-phased bulk samples. Single crystal structures were not collected due to the similar electron densities of 3+ 3+ Cr and Fe . Microscope images of K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O single crystals as well as K3[CrxFe1-x(ox)3]·2.5H2O single co-crystals grown from a solution containing an equimolar ratio of the two complexes are shown in Figure 55.

Figure 55: Microscope images showing the crystal habits and colours of pure K3[Cr(ox)3]·2.5H2O, K3[Fe(ox)3]·2.5H2O single crystals (a and b) and single co-crystals of the formula K3[CrxFe1-x(ox)3]·2.5H2O, which were grown from a solution containing a 1:1 ratio of K3[Cr(ox)3] and K3[Fe(ox)3] (c). The inset image (outlined in red) shows the same co-crystals rotated ca. 90° clockwise to highlight the blue iridescence of these crystals, which can be viewed at certain angles.

A sample of co-crystals from each of the five co-crystallisation experiments was harvested, deposited onto aluminium stubs and carbon-coated in preparation for II 2+ SEM-EDX analysis, in the same method as described for the [M (terpy)2] systems. At least three co-crystals from each experiment were analysed in at least three different areas by SEM-EDX giving a total of ca. 150 measurements. It was noted that the crystals looked cracked and weathered immediately after carbon-coating and completely crumbled after about 30 minutes under the vacuum of the SEM. Therefore, each stub was prepared and analysed before the following group of co-crystals was harvested from the mother liquor.

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The SEM-EDX results obtained for these samples were initially very confusing. Measurements from the same co-crystal were found to differ by amounts greater than what was seen for the systems previously investigated and what could be attributed to instrumental error. Regardless of the starting ratio of the two complexes in solution, the measurements taken from all of the co-crystals indicated the formation of a heterogeneous surface with respect to the Cr:Fe ratio.

The intracrystal variation of the chromium content (xsolid) ranged from 0.06-0.13 and

0.84-0.95 for co-crystals grown from solutions containing initial K3[Cr(ox)3] concentrations of 0.10 or 0.90 respectively. The range was larger at 0.19-0.35 and

0.59-0.77 for co-crystals grown from solutions containing initial K3[Cr(ox)3] concentrations of 0.30 and 0.70 respectively. The intracrystal surface variation observed for co-crystals grown from solutions containing an equimolar ratio of

K3[Cr(ox)3] and K3[Fe(ox)3] (xsolution = 0.50) was by far the most pronounced, with chromium xsolid values ranging from 0.40-0.95. The areas measured during these experiments were chosen at random. Furthermore, because only three areas were measured per crystal, it was not known if the various chromium xsolid values that were obtained were randomly distributed or the result of a concentration gradient. To test for a concentration gradient another co-crystallisation experiment was conducted. Since co-crystals with the greatest surface variation of metal ratios were grown from equimolar solutions, only this experiment was repeated (giving a total of four experiments where xsolution = 0.50). A total of ten co-crystals was analysed from this batch each in at least six different areas. The areas analysed were noted using an SEM image. Figure 56 shows an SEM image of a co-crystal grown from a solution containing an equimolar ratio of K3[Cr(ox)3] and K3[Fe(ox)3] and highlights the Cr:Fe ratio found and therefore the ratio between complexes for each of the areas outlined in the coloured boxes.

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ca. 0.90 K3[Cr(ox)3]

0.10 K3[Fe(ox)3] ca. 0.60 K3[Cr(ox)3]

0.40 K3[Fe(ox)3]

ca. 0.40 K3[Cr(ox)3] ca. 0.75 K3[Cr(ox)3] 0.60 K3[Fe(ox)3] 0.25 K3[Fe(ox)3]

Figure 56: SEM secondary electron image of a co-crystal grown from a solution containing an equimolar ratio of K3[Cr(ox)3] and K3[Fe(ox)3]. The Cr:Fe ratio found and therefore the ratio between complexes for each of the areas outlined in the coloured boxes is given. Areas outlined in red and yellow were found to be very rich in chromium. The areas outlined in green were found to have a slight excess of chromium whereas the area outlined in blue was found to be slightly deficient in chromium. Note also that the co-crystal appears to be cracked and weathered.

The results found for the co-crystal shown in Figure 56 infer the formation of a surface concentration gradient. The centre of the face (outlined blue) was the only area analysed that had a concentration bias in favour of K3[Fe(ox)3]. Areas nearest to the face centre (green outline) were analysed to have K3[Cr(ox)3] concentrations at about 60%. The areas outlined in yellow were found to have a K3[Cr(ox)3] concentration of 75% while those outlined in red were found to have 90%

K3[Cr(ox)3]. All of the other nine co-crystals that were analysed showed very similar results. None of the co-crystals had high levels of K3[Cr(ox)3] when analysed in the centre of the face nor were any shown to have high levels of K3[Fe(ox)3] at the face edges. As mentioned previously, the co-crystals appeared to deteriorate once placed under vacuum. Looking at Figure 56 it is interesting to note the columnar microstructure of these partially deteriorated co-crystals. This microstructure could be due to directional damage or represent evidence of columnar aggregation during crystal growth whereby each column is composed of the pure complex and the

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CHAPTER 5 relative frequency of each type of column determines the relative concentration of complexes found for a particular area.

The results obtained for these systems are very different to those that have been observed for binary co-crystallisation experiments previously undertaken during this work and during previous research undertaken by other members of the McMurtrie group.35,261,306,307 Over the past few years, investigations into the composition of crystals formed through binary co-crystallisation experiments have yielded one of four results. The first is the formation of crystals containing only one of the metal complexes that were present in solution. This occurs when the complexes being co-crystallised are too different to coexist in the same structure i.e. supramolecular selection leads to mutually exclusive crystallisation and is the premise behind the use of recrystallisation as a purification technique. It is important to note that this system involves complexes that have similar solubilities and hence is different from fractional crystallisation. Fractional crystallisation is a method that is commonly used to purify solutes based on differences in solubility whereby one solute is allowed to crystallise before the other. Mutually exclusive crystallisation as a result of extreme supramolecular selection was observed for experiments where [Ru(terpy)2](BF4)2 was co-crystallised with [Co(terpyO)(terpyOH)](BF4)2.

The second is the formation of stoichiometric co-crystals with respect to the ratio of metal complexes present in solution i.e. xsolid = xsolution. This is the opposite of the first scenario as the complexes being co-crystallised are indistinguishable to one another resulting in a system with negligible supramolecular selection. Systems where A B A [M (phen)3](PF6)2 complexes were co-crystallised with [M (phen)3](PF6)2 (M , MB = Fe, Ni, Co, Cu, Ru) showed no supramolecular selection and formed A B [M xM 1-x(phen)2](PF6)2 co-crystals where xsolid = xsolution.

The third is an intermediate of the former two systems where complexes being co-crystallised are similar enough to coexist in the same structure but different enough to instigate a selection bias during co-crystallisation resulting in a system that exhibits supramolecular selection where xsolid single co-crystal 1 ≠ xsolid single co-crystal 2. Examples of systems that displayed supramolecular selection are those where A B [M (bipy)3](PF6)2 complexes were co-crystallised with [M (bipy)3](PF6)2 and

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A B A B [M (terpy)2](PF6)2 complexes were co-crystallised with [M (terpy)2](PF6)2 (M , M = Fe, Ni, Co, Cu, Ru). In each of the three systems described, the individual co-crystals have a homogeneous concentration.

The fourth and the most complicated result that has been observed thus far is the formation of co-crystals that have homogeneous surface measurements that differ from surface measurements taken from other co-crystals from the same batch and also differ from measurements taken from the co-crystal’s interior. Therefore, in addition to exhibiting supramolecular selection these co-crystals also have a 3D concentration gradient, which is thought to be caused due to a slight solubility difference between the complexes being co-crystallised. Examples of systems that involved complexes that had slightly different solubilities and that displayed supramolecular selection are those where [Ru(terpy)2](BF4)2 complexes were II II co-crystallised with [M (terpyOH)2](BF4)2 (M = Fe, Ni, Cu).

Based on the SEM-EDX results for the co-crystal shown in Figure 56 and the nine other co-crystals analysed from this same experiment, it is evident that the composition of these co-crystals did not fit into any of these categories summarised here. To our knowledge, this is the first example of co-crystals that have formed with a concentration gradient on the surface. Since the co-crystals degrade under the vacuum of the SEM after about 30 minutes, further analysis of the surfaces using mapping techniques was not possible for co-crystals that had already been examined. Therefore, another replicate batch of co-crystals from an equimolar ratio of

K3[Cr(ox)3] and K3[Fe(ox)3] was co-crystallised in the same method as described earlier for the purpose of SEM-EDX 2D area mapping. However, it was realised that due to the vacuum of the SEM, the co-crystals deteriorated before the area map could be completed. The very short timeframe afforded by the SEM-EDX technique for the analysis of these co-crystals meant that only line maps spanning diagonally across the crystal face could be completed before the co-crystals collapsed. Since it was highly desirable to quantitatively characterise as much of the surface as possible, alternate methods capable of mapping were pursued.

Single crystal Raman spectroscopic mapping was found to be a suitable technique for the quantitative characterisation of these samples. The Raman spectra collected from

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K3[Fe(ox)3]·2.5H2O and K3[Cr(ox)3]·2.5H2O pure crystals were very similar, with the exception of a ca. 4 cm-1 difference in the position of the carbonyl stretching -1 frequency; 1722.97 and 1727.47 cm for pure K3[Fe(ox)3]·2.5H2O and

K3[Cr(ox)3]·2.5H2O respectively. Figure 57 highlights the separation of the carbonyl stretching bands of K3[Fe(ox)3]·2.5H2O and K3[Cr(ox)3]·2.5H2O.

Raman Spectra showing the difference in the carbonyl stretching peak position between K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O

K3[Fe(ox)3]·2.5H2O single crystals K3[Cr(ox)3]·2.5H2O single crystals x = 1722.97 cm-1 x = 1727.47 cm-1 s = 0.09 s = 0.09 n = 10 n = 10

powdered K3[Fe(ox)3]·2.5H2O powdered K3[Cr(ox)3]·2.5H2O

powdered K3[Cr(ox)3]·2.5H2O and K3[CrxFe1-x(ox)3]·2.5H2O

K3[Fe(ox)3]·2.5H2O (1:1 ratio) single co-crystal

Raman Intensity Intensity Raman Raman

17001700 17101710 17201720 17301730 17401740 17501750

-1 Wavenumber (cm ) Figure 57: Raman spectra highlighting the separation of the carbonyl stretching bands of -1 K3[Fe(ox)3]·2.5H2O and K3[Cr(ox)3]·2.5H2O at 1722.97 and 1727.47 cm respectively. The overlapping spectra shown in black were obtained from single crystals (10 from each K3[Fe(ox)3]·2.5H2O and K3[Cr(ox)3]·2.5H2O). The spectra shown in green and blue were acquired from powdered samples of pure crystals. The red spectrum was obtained from a single co-crystal exhibiting a surface concentration gradient grown from a solution containing a 1:1 ratio of the two complexes. The dotted spectrum was obtained from a powdered sample of a 1:1 ratio of the two compounds. All spectra shown have been normalised to aid comparison.

The black spectra shown were taken from single crystals of pure samples as a check of the instrument’s accuracy prior to each mapping session. The green and blue spectra were obtained from powdered samples of pure K3[Fe(ox)3]·2.5H2O and

K3[Cr(ox)3]·2.5H2O. The similarity of the spectra acquired from the powdered samples to those obtained from single crystals indicates that the crystal orientation has little effect on the spectral profile in this region. This figure also shows representative spectra from samples containing both metal complexes. The red spectrum shown was measured from a co-crystal exhibiting a surface concentration

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gradient and was grown from a solution containing an equimolar ratio of K3[Fe(ox)3] and K3[Cr(ox)3]. The spectrum represented by the dotted line was obtained from a sample containing a 1:1 ratio of the two compounds, which were ground together to form a fine powder. The peaks of both of these spectra which have a maxima at ca. 1725 cm-1 indicate the same ratio of the two compounds in the solid, however the spectrum of the powdered sample has a FWHM much greater than that of the co-crystal spectrum. A total of eight measurements were made from the manually combined powdered sample all of which had peaks with similar FWHM to the example spectrum shown. Similarly, the peak widths calculated for all of the co-crystal measurements (hundreds) were of similar size to the red peak shown in Figure 57. These results strongly indicate that the position of the carbonyl stretching frequency in the Raman spectra of co-crystals is not simply a superposition of the two peaks but instead a single crystal characteristic that could be exploited to gain quantitative information i.e. the position of the peak is indicative of the ratio of the two complexes in the co-crystals. The differences between the peak widths also renders the notion of crystal growth via columnar aggregation i.e. aggregation of columns composed of pure complex as highly unlikely. Instead, these results strongly suggest that the concentration gradient observed is a change that occurs at the molecular level and that the microstructure observed is likely a result of directional damage because of the harsh condiditons in the SEM. Although beyond the scope of this project, it would be interesting to investigate the composition of these types of co-crystals at the nanoscale level using higher resolution characterisation techniques.

Using the position of this very prominent carbonyl stretching band in the Raman spectrum, it was possible to measure and map the ratio of K3[Cr(ox)3]·2.5H2O to

K3[Fe(ox)3]·2.5H2O at a particular point on the co-crystal surface. This technique was validated by first mapping the frequency of the carbonyl stretching peak and then conducting another map along the same transect using SEM-EDX. Five co-crystals were characterised using both techniques for the purpose of validating the use of Raman spectroscopy as a qualitative characterisation technique for these samples. One of the co-crystals analysed using Raman spectroscopy and SEM-EDX is shown in Figure 58. The transect followed during Raman mapping is represented by the dotted line between points A and B. The co-crystal region around B had deteriorated by the time the EDX mapping software was programmed to analyse it.

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Therefore, no data were collected for this region resulting in a shorter transect for the SEM-EDX map compared to the one collected using Raman. The results from both Raman and SEM-EDX line maps are shown in Figure 59 and Figure 60 respectively.

ca. 0.90 K3[Cr(ox)3] ca. 0.40 K3[Cr(ox)3] 0.10 K3[Fe(ox)3] 0.60 K3[Fe(ox)3]

B

A

100 100 µm

200 µm Figure 58: Microscope image of a single co-crystal exhibiting a concentration gradient that was co-crystallised from a solution containing an equimolar ratio of K3[Cr(ox)3] to K3[Fe(ox)3]. The transect followed during Raman mapping is represented by the black dotted line between the points marked A and B. The transect followed during SEM-EDX mapping (diagonally from A to B) was shorter as the edge marked B had deteriorated under the SEM atmosphere. The ratios between the complexes shown in the red and blue boxes were calculated using Raman carbonyl peak positions.

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Distance along transect vs. Raman peak position on the surface of a co-crystal grown from a solution containing a 1:1 ratio of K3[Cr(ox)3] and K3[Fe(ox)3]

1727.41727.4 O

0.95 O 2

95 2 2.5H

1727.0 2.5H ·

1727.0 ·

] ] ]

3 3 )

) 0.85 1

1 85

- -

1726.61726.6

[Cr(ox) [Cr(ox) 3 750.75 3 1726.21726.2 0.6565 1725.81725.8

0.5555

1725.4 Raman peak position (cm position peak Raman Raman peak position (cm 1725.4 position peak Raman

0.45

1725.01725.0 45

Estimated molar fraction of K K of of fraction fraction molar molar Estimated Estimated

1724.61724.6 0.3535 0 100 200 300 400 500 600 700 800 900 A Distance along transect (µm) B Figure 59: Plot of the Raman peak position across the transect shown on the single co-crystal in Figure 58 that was grown from a solution containing a 1:1 ratio of K3[Cr(ox)3] to K3[Fe(ox)3]. A scale of the estimated molar fraction of K3[Cr(ox)3]·2.5H2O as derived from the Raman peak shifts is shown on the secondary y axis on the right.

Distance along transect vs. fraction of Cr detected by EDX on the surface of a co-crystal 2 5 8 11 14 17 20 23 26 29 32 35 38 41 44 47 50 53 grown from a solution containing a 1:1 ratio of K3[Cr(ox)3] and K3[Fe(ox)3] 1.001 1

0.90.90 1

0.80.80 1

0.70.70 solid

solid 1

x x Cr Cr Cr Cr 0.60.60 1

0.50.50 1

0.40.40 0

0.30.30 0 100 200 300 400 500 600 700 800 9000 A Distance along transect (µm) B Figure 60: Plot of the EDX measurements across the transect shown on the single co-crystal in Figure 58. The co-crystal had deteriorated by the time the EDX mapping software was programmed to analyse the region around B. Therefore, no data was collected for this region resulting in a shorter transect for the SEM-EDX map compared to the one collected using Raman.

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Both of the plots shown in Figure 59 and Figure 60 indicate increasing concentrations of K3[Cr(ox)3]·2.5H2O moving towards the edge of the co-crystal at concentrations of ca. 86% and show a minimum at about halfway along the transect corresponding to a relative K3[Cr(ox)3]·2.5H2O concentration of ca. 36%. It is important to note that although transects for both maps traversed the same general path on the co-crystal surface, it was difficult to take measurements at exactly the same points due to experimental and instrumental limitations. Furthermore, SEM-EDX maps were usually collected 12-24 hours after the Raman measurements were completed, at which time the co-crystal surface had started to show visible signs of deterioration. Penetration depths are yet another factor that was expected to be slightly different due to the inherent differences between the two techniques; Raman scattering of monochromatic visible light versus X-ray excitation and the need to carbon-coat prior to SEM-EDX. Despite all of these factors, it is very interesting that both techniques produced maps with very similar profiles that have aberrations occurring in very similar positions on the co-crystal surface. The results from all of the co-crystals used to validate the Raman spectroscopic mapping technique for quantitative analysis indicated a strong correlation between the peak position of the carbonyl stretching frequency and relative concentration of the metal complexes. These results along with the non-destructive analysis afforded by Raman compared to SEM-EDX, established Raman mapping as the preferred primary quantitative characterisation technique for the analysis of additional co-crystals of this type.

In addition to the five co-crystals used to validate the Raman technique for quantitative use, another 10 co-crystals from two additional replicate batches were analysed by Raman mapping. The surface of each co-crystal was mapped along a diagonal transect (similar to Figure 58) and over an area that spanned as much of the surface as possible. Figure 61 shows the graphical results from a Raman area map conducted on the same surface of the same co-crystal, which is shown in Figure 58.

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Figure 61: Graphical representations of the data derived from a Raman area map conducted on the surface of a single co-crystal. The image on the left shows the discrete areas analysed overlaid on the microscope image of the co-crystal. The image on the right is a smoothed 3D representation of the same data. The colour-coded scale used in both images is also shown (far right). The map results indicate higher relative concentrations of K3[Cr(ox)3]·2.5H2O at the crystal’s edges (red/yellow areas) than present in the centre (purple/blue).

The results shown in Figure 61 were typical of all maps conducted on each of the co-crystals analysed. All results (both SEM-EDX and Raman) indicated that the formation of a 2D directional surface concentration gradient was ubiquitous among co-crystals grown from solutions containing a 1:1 ratio of K3[Cr(ox)3] and

K3[Fe(ox)3]. Using the Raman peak shifts to estimate the molar fractions at various * areas mapped, it was found that K3[Cr(ox)3]·2.5H2O concentrations gradually increased from ca. 35-40% at the face centre to ca. 85-90% at the co-crystal edge. At no point on any co-crystalline surface was the relative concentration of

K3[Cr(ox)3]·2.5H2O lower than ca. 30%. This suggests that K3[Fe(ox)3] is slightly less soluble than K3[Cr(ox)3] and therefore begins to crystallise first under the conditions of these co-crystallisations. Therefore, it was postulated that due to the apparent subtle solubility difference between the two complexes being co-crystallised, that even lower relative concentrations of K3[Cr(ox)3]·2.5H2O, perhaps even the co-crystal origin (i.e. 100% K3[Fe(ox)3]·2.5H2O) was present somewhere below the surface.

Two methods were attempted at exposing a cross-section perpendicular to the previously mapped external surface. The first involved manually cutting the

*Molar fractions derived from Raman peak shifts were calculated using a calibration curve where the shifts of pure K3[Fe(ox)3]·2.5H2O and K3[Cr(ox)3]·2.5H2O equate to a relative K3[Cr(ox)3]·2.5H2O concentration of 0 and 100% respectively.

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CHAPTER 5 co-crystal under an optical microscope using a scalpel. The second involved embedding the co-crystal in epoxy resin, followed by microplaning away several hundred micrometres. In principle, the latter method was ideal as several cross-section maps could be conducted at different depths resulting in a 3D point-specific elemental analysis of the co-crystal. However, both methods were found to be unsuitable as the co-crystals crumbled.

Estimates of the K3[Cr(ox)3]·2.5H2O concentration at various depths below the surface were instead derived from spectra obtained through confocal Raman spectroscopy. Confocal Raman spectra were collected for five co-crystals that had already been surface-mapped. The results from the surface measurements from each of the five co-crystals were very similar. Given the time-sensitive viability of co-crystals and that each confocal experiment required 15-20 hours to complete, only one depth-profile map was collected for each co-crystal. Three co-crystals were mapped along transects with trajectories that were parallel to the surface previously mapped, while two co-crystals were depth-profiled along transects that were perpendicular to the surface maps.

The co-crystal shown in Figure 58 was one of the co-crystals mapped using this technique. A plot of the depth versus the change in the confocal Raman peak position is shown in Figure 62. The 0 µm measurement (surface) was taken from the adjacent face to the one previously analysed about 100 µm in from the longest edge, so that the trajectory of the transect was parallel to the largest facet (the face previously mapped on the surface). Spectra were collected every 20 µm to depths of up to 500 µm below the surface (duration ca. 20 hours). A schematic diagram of the co-crystal analysed is shown as an inset to illustrate the relationship between the two faces and the trajectory of the confocal map (black single-headed arrow). A scale of the estimated molar fraction of K3[Cr(ox)3]·2.5H2O as derived from the Raman peak shifts (using the same calibration curve as for Figure 59) is shown on the secondary y axis on the right.

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Depth vs. Confocal Raman peak position

1725.6 0.58 O

1725.5 0.56 2

)

1 -

0.54 ·2.5H ] 1725.4 3

0.52

1725.3

[Cr(ox) 3 0.50 1725.2 0.48 1725.1 0.46 1725.0 0.44

1724.9

0.42 Confocal Raman peak position peak (cmposition Raman Confocal

1724.8 0.40 Estimated molar fraction of molarof fraction EstimatedK

1724.7 0.38 0 -100 -200 -300 -400 -500 0 -100 -200 -300 -400 -500 Depth (µm) Figure 62: A plot of the depth versus the change in the confocal Raman peak position. A schematic diagram of the co-crystal analysed is shown as an inset to illustrate the dimensions and the relationship between the face that was previously surface mapped (largest facet outlined in red) and the starting surface position of the depth-profile map (solid arrow through the face shaded in grey). A scale of the estimated molar fraction of K3[Cr(ox)3]·2.5H2O as derived from the Raman peak shifts is shown on the secondary y axis on the right.

The confocal data presented in Figure 62 suggest a steady decrease of the

K3[Cr(ox)3]·2.5H2O concentration moving from the surface (ca. 57%) to a depth of about 360 µm (39%) and then a slight increase from depths of 360-500 µm below the surface. The K3[Cr(ox)3]·2.5H2O concentrations calculated from the confocal data suggest a similar yet less pronounced concentration gradient (Δ 20%) to that found on the surface (Δ 50%). The minimum K3[Cr(ox)3]·2.5H2O concentration at about -360 µm approximately corresponds to the half-way point along the face outlined in red in the schematic shown in Figure 62; the area where the minimum

K3[Cr(ox)3]·2.5H2O concentration was found on the surface. The slight increase in the K3[Cr(ox)3]·2.5H2O concentration from depths of 360-500 µm also mimic the trend observed from the areas map collected on the surface (Figure 61). Two other co-crystals were mapped using confocal microscopy along depth-transects that were parallel to their largest facet in approximately similar positions from the edges. The results of both depth-profiles closely resemble the data presented in Figure 62.

Figure 63 is a plot of the depth versus the change in the confocal Raman peak position acquired from two maps obtained from two different co-crystals. Spectra

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CHAPTER 5 were collected every 10 µm to depths of up to 250 µm below the surface. The depth-transects of the confocal maps for these two co-crystals had trajectories that were perpendicular to the faces on which the surface mapping data were previously collected. A schematic diagram illustrating the relationship between the face previously mapped on the surface (red outlined face) and the starting positions (0 µm) of the two confocal maps is shown as an inset in Figure 63. The data obtained from the centre of one co-crystal (solid arrow) are plotted with the solid line, whereas the data collected closer to the edge from another co-crystal (dashed arrow) are plotted with the dotted line. Since both co-crystals had similar dimensions, only one schematic is shown. As with previous plots, the scale of the estimated molar fraction of K3[Cr(ox)3]·2.5H2O corresponding to the Raman peak shifts is shown on the secondary y axis on the right.

Depth vs. Confocal Raman peak position

1726.21726.2 0.700.70 O

1726.0 O 2 1726 2

0.650.65

) )

1 1

- -

2.5H 2.5H ·

1725.81725.8 ·

] ] ] 3 0.600.60 3 1725.61725.6

0.55 [Cr(ox)

0.55 [Cr(ox)

3 3 1725.41725.4 1 mm 0.500.50 1725.21725.2

m 0.450.45 1725.01725 µ

300 0.400.40

1724.81724.8

Confocal Raman peak position (cm (cm position position peak peak Raman Raman Confocal Confocal

1724.61724.6 0.350.35

Estimated molar fraction of K K of of fraction fraction molar molar Estimated Estimated 1724.41724.4 0.300.30 0 -50-50 -100-100 -150-150 -200-200 -250-250 Depth (µm) Figure 63: A plot of the depth versus the change in the confocal Raman peak position acquired from two depth-profile maps from two different co-crystals exhibiting surface concentration gradients. A schematic diagram representing the co-crystals analysed is shown as an inset to illustrate the dimensions and the relationship between the face that was previously surface mapped (outlined in red) and the starting surface position of the confocal map (shaded in grey). The profile obtained from the centre of one co-crystal (solid arrow) is plotted with the solid line, whereas the data collected closer to the edge from another co-crystal (dashed arrow) is plotted with the dotted line. The scale of the estimated molar fraction of K3[Cr(ox)3]·2.5H2O corresponding to the Raman peak shifts is shown on the secondary y axis on the right.

The variation in the K3[Cr(ox)3]·2.5H2O concentration along each respective transect shown in Figure 63 is very minimal at less than 0.10, compared to the variations obtained from the parallel depth-profiles (Δ 0.20) and the surface maps (Δ 0.50). The

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depth-profile originating from the face centre suggests lower K3[Cr(ox)3]·2.5H2O concentrations below the surface at depths around 75-175 µm. The minimum values for upper trace do not occur mid-way through the transect, but instead occur at lower depths, from about 125-200 µm through the co-crystal. This could be due to the rhombohedral habit of the co-crystals, as the 0 µm (surface) measurement is closer to the crystal edge of the upper face compared to the proximity of the 250 µm measurement to the edge of the opposing face. The results from both of these depth-profiles indicate only a very subtle concentration gradient is present between the two large faces of these co-crystals.

All of the co-crystals characterised using Raman mapping were found to have large concentration gradients on the surface with concentrations of K3[Cr(ox)3]·2.5H2O of 90% and 40% at the surface edges and centre respectively. Depth-profiles parallel to the large face acquired through confocal experiments, showed K3[Cr(ox)3]·2.5H2O concentrations and changes that had the same trend to that found on the surface. Concentrations derived from depth-profiles perpendicular to the large faces were found to be relatively constant or vary only slightly. Information gained from all of the quantitative characterisation experiments suggests favourable propagation of crystal growth in some directions but not others during co-crystallisation. Although it was postulated earlier that the growth of these co-crystals is due to fractional crystallisation and/or supramolecular selection, the exact reasons for these observations are not clear from these experiments.

To gain a better understanding into the mechanisms driving the results obtained for co-crystals grown from solutions containing equimolar ratios of K3[Cr(ox)3] and

K3[Cr(ox)3], several epitaxial crystallisation experiments were conducted. Epitaxial III III crystals were formed by immersing K3[M (ox)3]·2.5H2O seed crystals (M = Cr III III and/or Fe) into saturated solutions of K3[M (ox)3](aq/EtOH) (M = Cr or Fe). Immersion of seed crystals was achieved by either placing the crystals directly in the vial containing the saturated solution or by first adhering the seed crystals to a glass fibre and then suspending them in solution. The goal of these experiments was to form epitaxial growth crystals with well-defined domains containing either

K3[Cr(ox)3]·2.5H2O or K3[Fe(ox)3]·2.5H2O. Since K3[Cr(ox)3]·2.5H2O crystals are dark blue/green and crystals of K3[Fe(ox)3]·2.5H2O are bright green, the epitaxial

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CHAPTER 5 crystals and their domains were easily distinguished by eye from the pure crystals that also formed during the experiment. Table 18 summarises the composition of the seed crystals and saturated solutions used to form epitaxial crystals. Each epitaxial experiment was repeated at least once to ensure reproducibility giving a total of at least 16 experiments. A brief description of the method used to form and prepare seed crystals and to prepare saturated solutions is provided as a footnote at the base of the table. It is important to note that only saturated solutions were used to avoid dissolution of the seed.

Table 18: Summary of the composition of the seed crystals and the saturated solutions used to crystallise epitaxial growth crystals.

Epitaxial * † Seed crystal(s) Sat. solution(aq/EtOH) system

1 K3[Fe(ox)3]·2.5H2O K3[Cr(ox)3]

2 K3[Cr(ox)3]·2.5H2O K3[Fe(ox)3]

3 K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O K3[Cr(ox)3]

4 K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O K3[Fe(ox)3] * Seed crystals were grown as per the vapour diffusion recrystallisation method (EtOH into H2O). † Saturated solutions were prepared by first dissolving the appropriate metal complex in H2O and then quickly adding EtOH until the first sign of precipitation. The solution was then filtered through a nylon filter fitted to a syringe. Saturated solutions were used immediately and any excess discarded.

The first epitaxial system described in Table 18 can be described as a discrete version of K3[CrxFe1-x(ox)3]·2.5H2O co-crystals that spontaneously formed with surface concentration gradients. Instead of a gradient increase in the

K3[Cr(ox)3]·2.5H2O relative concentration from the surface centre toward the edge, these epitaxial crystals have an abrupt change of concentration from one domain to the next. Figure 64 shows microscope images of an intact epitaxial crystal resulting from placing a K3[Fe(ox)3]·2.5H2O seed into a saturated solution of

K3[Cr(ox)3](aq/EtOH).

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-90°

1 mm 1 mm Figure 64: Optical microscope images of one epitaxial crystal grown by immersing a K3[Fe(ox)3]·2.5H2O seed into a saturated solution of K3[Cr(ox)3](aq/EtOH). The crystal in the image on the right was rotated ca. 90° anticlockwise to highlight the blue iridescence of the K3[Cr(ox)3]·2.5H2O domain that can be viewed at certain angles. It is important to note that these images are of an intact crystal and not of cross-section slices.

As mentioned throughout this section none of the K3[CrxFe1-x(ox)3]·2.5H2O co-crystals that spontaneously formed with surface concentration gradients showed higher amounts of K3[Cr(ox)3]·2.5H2O at the surface centre than at the surface edge. Therefore, epitaxial crystals resulting from the second system described in Table 18 have surface centre and edge concentrations that are the inverse of what was observed to occur spontaneously from solutions that contained both complexes. Figure 65 shows microscope images of an intact epitaxial crystal resulting from placing a K3[Cr(ox)3]·2.5H2O seed into a saturated solution of K3[Fe(ox)3](aq/EtOH).

180°

1 mm 1 mm Figure 65: Optical microscope images of one epitaxial crystal grown by immersing a K3[Cr(ox)3]·2.5H2O seed into a saturated solution of K3[Fe(ox)3](aq/EtOH). The crystal in the image on the right was flipped to show the underside. It is important to note that the crystal shown in this figure is intact not a cross-section slice.

Although the seeds were all of different sizes and slightly different shapes due to the different habits exhibited by K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O, all had large faces on opposing sides of the crystals, that are denoted as the top and underside for the purposes of describing epitaxial growth. Looking at the epitaxial

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CHAPTER 5 crystals shown in Figure 64 and Figure 65 it is evident that the epitaxial growth occurs in a preferred orientation with respect to the seed substrate. From these images, it does not seem that any epitaxial growth has occurred on either the top or underside of the seed. Growth for both systems seemed to have only occurred around the perimeter of the seed. Characterisation of the seed domain by Raman microscopy and SEM-EDX spot analysis confirmed that no epitaxial growth occurred on the top or underside of the seed, while analysis of the epitaxial growth domain indicated only the presence of the complex that was present in the growth solution. The surfaces of epitaxial crystals were also characterised using Raman spectroscopic line mapping. The results from line maps obtained from two representative epitaxial crystals (one from each system) are shown in Figure 66 and Figure 67. The transects spanned across the seed domain and the epitaxial growth on either side of the seed (on the same face). Measurements were collected at intervals of 20 µm.

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Distance along transect vs. Raman peak position on the surface of an epitaxial crystal

grown by immersing a K3[Fe(ox)3]·2.5H2O seed into a K3[Cr(ox)3] solution

1727.51727.5 1.001

O O 2

1727.01727.0 0.900.9 2

2.5H 2.5H ·

0.80 · ] ]

0.8 ] 3

1726.5 3 )

1726.5)

1 1

- - 0.700.7

1726.01726.0

[Cr(ox) [Cr(ox)

3 3 0.600.6 1725.51725.5 0.500.5 1725.01725.0 0.400.4 1724.51724.5

0.300.3

Raman peak position (cm (cm position position peak peak Raman Raman 1724.0 1724.0 0.200.2

1723.51723.5 0.100.1

Estimated molar fraction of K K of of fraction fraction molar molar Estimated Estimated

1723.01723.0 0.000 0 200 400 600 800 1000 1200 1400 1600 1800 Distance along transect (µm) Figure 66: The Raman peak positions across a transect from an epitaxial crystal grown by immersing a K3[Fe(ox)3]·2.5H2O seed into a solution of K3[Cr(ox)3](aq/EtOH). Measurements were taken every 20 µm. A scale of the estimated molar fraction of K3[Cr(ox)3]·2.5H2O as derived from the Raman peak shifts is shown on the secondary y axis on the right.

Distance along transect vs. Raman peak position on the surface of an epitaxial crystal

grown by immersing a K3[Cr(ox)3]·2.5H2O seed into a K3[Fe(ox)3] solution

1727.51727.5 1.001

O O 2

1727.01727.0 0.90.90 2

2.5H 2.5H ·

0.80 · ] ]

0.8 ] 3

1726.5 3 )

1726.5)

1 1

- - 0.70.70

1726.01726.0

[Cr(ox) [Cr(ox)

3 3 0.600.6 1725.51725.5 0.500.5 1725.01725.0 0.40.40 1724.51724.5

0.300.3

Raman peak position (cm (cm position position peak peak Raman Raman 1724.0 1724.0 0.200.2

1723.51723.5 0.100.1

Estimated molar fraction of K K of of fraction fraction molar molar Estimated Estimated

1723.01723.0 0.000 0 200 400 600 800 1000 1200 1400 Distance along transect (µm) Figure 67: The Raman peak positions across a transect from an epitaxial crystal grown by immersing a K3[Cr(ox)3]·2.5H2O seed into a solution of K3[Fe(ox)3](aq/EtOH). Measurements were taken every 20 µm. A scale of the estimated molar fraction of K3[Cr(ox)3]·2.5H2O as derived from the Raman peak shifts is shown on the secondary y axis on the right.

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Figure 66 shows the Raman peak position along a transect on the surface of a crystal grown by immersing a K3[Fe(ox)3]·2.5H2O seed into a solution of

K3[Cr(ox)3](aq/EtOH). Figure 67 shows the Raman peak positions along a transect on the surface of a crystal grown by immersing a K3[Cr(ox)3]·2.5H2O seed into a -1 solution of K3[Fe(ox)3](aq/EtOH). Peaks at 1723.0 cm indicate a K3[Cr(ox)3]·2.5H2O -1 fraction of 0%. Conversely, peaks at 1727.5 cm signify a K3[Cr(ox)3]·2.5H2O content of 100%. Looking at the profile in Figure 66, it is evident that the seed domain (between 500-1300 µm) is composed of pure K3[Fe(ox)3]·2.5H2O, while the peak positions between 0-250 µm and 1450-1800 µm along the transect indicate the presence of only K3[Cr(ox)3]·2.5H2O. The profile in Figure 67 suggests that the

K3[Cr(ox)3]·2.5H2O content is 100% between 600-800 µm (seed domain) and 0% at the outer regions of the transect between 0-300 µm and 1200-1500 µm.

These results are consistent with those found by Raman and SEM-EDX spot analysis. The change in the K3[Cr(ox)3]·2.5H2O content between the seed domain and the epitaxial domains is much more gradual in Figure 67 than for the trace in Figure 66. The results presented here suggest the interface between the seed and epitaxial domains is about 150 µm larger for crystal represented in Figure 67. This indicates a more diffuse interface is present for crystals grown from

K3[Cr(ox)3]·2.5H2O seeds immersed in saturated solutions of K3[Fe(ox)3](aq/EtOH) than vice versa. This is likely due to the slight difference in the solubilities of the complexes resulting in greater partial dissolution of the K3[Cr(ox)3]·2.5H2O than

K3[Fe(ox)3]·2.5H2O. Notwithstanding this slight complication, the profiles of the two curves shown in Figure 66 and Figure 67 appear to be the inverse of each other.

When the seed crystals were first attached to a glass fibre and then immersed in the growth solution, the results were markedly different to those observed when the seeds were allowed to rest at the base of the vial. Microscope images of a

K3[Cr(ox)3]·2.5H2O seed crystal suspended in a solution of K3[Fe(ox)3](aq/EtOH) by a glass fibre before and after epitaxial growth, and an epitaxial crystal resulting from a

K3[Fe(ox)3]·2.5H2O seed crystal suspended in a K3[Cr(ox)3](aq/EtOH) solution are shown in Figure 68. In the reverse experiment, the suspended K3[Fe(ox)3]·2.5H2O seed was not easily visible through the dark green/blue K3[Cr(ox)3](aq/EtOH) solution,

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CHAPTER 5 therefore only a microscope image of the resulting epitaxial crystal is shown in this figure.

(a) (b)

(c)

1 mm

Figure 68: Images of a K3[Cr(ox)3]·2.5H2O seed suspended by a glass fibre in a solution containing K3[Fe(ox)3](aq/EtOH) before (a) and after (b) epitaxial growth. The image on the right (c) is of an epitaxial crystal resulting from a K3[Fe(ox)3]·2.5H2O seed suspended by a glass fibre in a solution containing K3[Cr(ox)3](aq/EtOH).

Looking at the crystals shown in Figure 68, it is clear that epitaxial growth occurred on all faces of the seed substrate resulting in a completely enveloped seed. Characterisation of areas on the surface using Raman and SEM-EDX showed that the surface on all sides was composed entirely of the complex that was present in the growth solution. The differences between the epitaxial crystals resulting from the two methods of introducing the seed into the solution are quite remarkable. It seems that epitaxial growth is only allowed around the perimeter of the seed when either the top or underside of the seed is in contact with the base of the glass vial. The reasons for this observation are not known but are thought to be attributed to local charging effects occurring between the crystalline material and the glass of the vial during crystallisation. The same effects could be present during the growth of

K3[CrxFe1-x(ox)3]·2.5H2O co-crystals, where concentration gradients were observed to be highly pronounced in some directions but not others.

The two experiments that involved immersing seed crystals of each of

K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O into solutions of either

K3[Cr(ox)3](aq/EtOH) or K3[Fe(ox)3](aq/EtOH) were designed to test the selection process for like and different complex molecules in solutions already containing crystals of the same composition as the solution. Figure 69 shows seed crystals of

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K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O suspended by glass fibres and immersed in a solution of K3[Fe(ox)3](aq/EtOH) at the commencement of the experiment. A photo of the crystals immersed in a saturated solution of

K3[Cr(ox)3](aq/EtOH) is not shown due to the dark colour of the solution obscuring the crystals from view. Epitaxial growth was observed to occur on both types of crystals in each experiment suggesting that the supramolecular interactions between the like and different complexes are comparable. Epitaxial crystals that resulted when seeds were allowed to settle to the base of the vial showed the same perimeter growth pattern that was observed when only one type of seed was introduced. Similarly, seeds that were suspended by a glass fibre were completely enveloped by epitaxial growth akin to the crystals from single seed experiments.

Figure 69: Seed crystals of K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O suspended by glass fibres and immersed in a solution of K3[Fe(ox)3](aq/EtOH).

An additional experiment was conducted where K3[Fe(ox)3]·2.5H2O seeds were immersed in a saturated solution containing an equimolar ratio of K3[Cr(ox)3] and

K3[Fe(ox)3]. SEM-EDX of the triturated solid material that formed during the preparation of the saturated solution was found to contain ca. 1:1 ratio of the two complexes (xsolid = 0.51 ± 0.02) indicating that the resulting saturated solution also contained an equimolar ratio of both complexes. This experiment was designed to observe if co-crystals with a concentration gradient would form when a pure

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K3[Fe(ox)3]·2.5H2O seed crystal was placed in a saturated solution containing an equimolar ratio of both complexes. By using a saturated solution, the solubility differences between the two complexes are minimised and therefore any concentration gradient that formed could be largely attributed to supramolecular selection, a bias for K3[Fe(ox)3] due to the seed rather than just fractional crystallisation. Figure 70 shows microscope images of an intact epitaxial crystal resulting from placing a K3[Cr(ox)3]·2.5H2O seed into a saturated solution containing an equimolar ratio of K3[Cr(ox)3] and K3[Fe(ox)3]. Figure 71 plots the Raman peak position along a transect that spanned across the seed domain and the epitaxial growth on either side (on the same face). Measurements were taken at 20 µm intervals.

-90°

1 mm 1 mm Figure 70: Optical microscope images of an epitaxial crystal grown by immersing a K3[Fe(ox)3]·2.5H2O seed into a saturated solution containing an equimolar ratio of K3[Cr(ox)3] and K3[Fe(ox)3]. The crystal in the image on the right was rotated ca. 90° anticlockwise to highlight the blue iridescence of the K3[Cr(ox)3]·2.5H2O present in the epitaxial growth domain that can be viewed at certain angles. It is important to note that these images are of an intact crystal and not of cross-section slices.

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Distance along transect vs. Raman peak position on the surface of an epitaxial crystal

grown by immersing a K3[Fe(ox)3]·2.5H2O seed into a solution containing a 1:1 ratio of K3[Cr(ox)3] and K3[Fe(ox)3]

1727.51727.5 1.001

O O 2

1727.01727.0 0.900.9 2

2.5H 2.5H ·

0.80 · ] ]

0.8 ] 3

1726.5 3 )

1726.5)

1 1

- - 0.700.7

1726.01726.0

[Cr(ox) [Cr(ox)

3 3 0.600.6 1725.51725.5 0.500.5 1725.01725.0 0.400.4 1724.51724.5

0.300.3

Raman peak position (cm (cm position position peak peak Raman Raman 1724.0 1724.0 0.200.2

1723.51723.5 0.100.1

Estimated molar fraction of K K of of fraction fraction molar molar Estimated Estimated

1723.01723.0 0.000 0 200 400 600 800 1000 1200 Distance along transect (µm) Figure 71: Plot of the Raman peak position across a transect on a crystal grown from a K3[Fe(ox)3]·2.5H2O seed immersed in a solution containing an equimolar ratio of K3[Cr(ox)3] and K3[Fe(ox)3]. A scale of the estimated molar fraction of K3[Cr(ox)3]·2.5H2O as derived from the Raman peak shifts is shown on the secondary y axis on the right.

The profile of the graph shown in Figure 71 indicates a seed domain containing pure

K3[Fe(ox)3]·2.5H2O from about 500-750 µm along the transect. This seed domain is flanked by epitaxial growth that appears to have a concentration gradient not unlike the gradient observed for K3[CrxFe1-x(ox)3]·2.5H2O co-crystals. At no point along the transect or any point found through spot analysis was an area containing 100 %

K3[Cr(ox)3]·2.5H2O found. It is interesting that despite the solution containing both

K3[Cr(ox)3] and K3[Fe(ox)3] in ca. 1:1 ratio, the epitaxial growth that initially forms is biased in favour of K3[Fe(ox)3]·2.5H2O. Without any significant solubility differences between the complexes in the saturated solution and the possibility of major partial dissolution of the seed substrate (as indicated by Figure 66), this indicates that supramolecular selection is a likely mechanism occurring during the co-crystallisation of K3[Cr(ox)3] and K3[Fe(ox)3]. In fact, the plot shown in Figure 71 looks like a hybrid between the graph shown in Figure 66 and the graph shown in Figure 59.

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II I III 5.2.2 Co-ordination frameworks of the type [M (L)3][M M (ox)3]

Three-dimensional metal-organic frameworks with the general formula II I III [M (L)3][M M (ox)3] ( L = 2,2′-bipyridine, 1,10-phenanthroline) have been known

364 since 1971 and tend to crystallise in cubic space groups such as P213 and P4332. Since then, many coordination frameworks of this type have been synthesised to II I III yield similar structures. Interestingly, there are many more [M (L)3][M M (ox)3] II 2+ type structures in the literature that contain [M (bipy)3] than those that contain II 2+ [M (phen)3] . Table 19 summarises the crystal structures of coordination frameworks that are available in the CSD with the general formula II I III II/III z+ [M (L)3][M M (ox)3] or similar structures involving [M (L)3] with I III 2- II III - II 2- I III 2- {[M M (ox)3] }n , {[M M (ox)3] }n, {[M 2(ox)3] }n or {[M M (dto)3] }n, (L = 2,2′-bipyridine, 1,10-phenanthroline, ox = oxalato, dto = 1,2-dithiooxalato).51 Unless it was indicted that enantiopure starting materials were used, the chirality indicated in Table 19 is a result of spontaneous resolution during crystallisation from racemic starting materials. Therefore, the bulk samples obtained from racemic starting materials would contain both Δ and Λ single crystals.

.

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Table 19: Summary of crystal structures (in chronological order of publication) and crystallising II/III z+ I III 2- conditions of 3D coordination frameworks involving [M (L)3] with either {[M M (ox)3] }n, II III - II 2- I III 2- {[M M (ox)3] }n, {[M 2(ox)3] }n or {[M M (dto)3] }n, (L = 2,2′-bipyridine, 1,10-phenanthroline and ox = oxalato, dto = 1,2-dithiooxalato).

CSD Space Cell Crystallising Year Compound Formula Chirality REFCODE Group Dimensions Conditions

S.D. Me2CO /H2O (5ºC) * II III a = PNIOCO 1971 [Ni (phen)3][KCo (ox)3]·2H2O P213 Λ using 16.225(10) enantiomerically pure complexes * II II + YAPPAG 1993 [Fe (bipy)3][Fe 2(ox)3] P4332 a = 15.392(2) Δ S.E. H2O/H3O , λUV * II II HEYTIO 1994 [Ni (bipy)3][Mn 2(ox)3] P4132 a = 15.579(2) Λ Gel S.D. H2O HEYTOU* 1994 [FeII(bipy) ][NaFeIII(ox) ] P2 3 a = 15.507(3) Λ 3 3 1 Gel S.D. H2O HEYTUA* 1994 [FeII(bipy) ][LiCrIII(ox) ] P2 3 a = 15.262(4) Λ 3 3 1 Gel S.D. H2O * II III TUNFAJ 1996 [Ni (bipy)3][NaAl (ox)3] P213 a = 15.518(2) Λ Gel S.D. H2O * III III ZUQVAI 1996 [Cr (bipy)3][NaCr (ox)3]ClO4 P213 a = 15.523(4) Λ Gel S.D. H2O ZUQVEM* 1996 [CrIII(bipy) ][MnII (ox) ]ClO P4 32 a = 15.564(3) 3 2 3 4 1 Λ Gel S.D. H2O ZUQVIQ* 1996 [CrIII(bipy) ][MnII (ox) ]BF P4 32 a = 15.564(3) 3 2 3 4 1 Λ Gel S.D. H2O ZUQVOW* 1996 [CoIII(bipy) ][NaCrIII(ox) ]PF P2 3 a = 15.515(3) Δ 3 3 6 1 Gel S.D. H2O a = 16.238(4) * II III ZUQVUC 1996 [Ni (phen)3][NaCo (dto)3]·Me2CO P212121 b = 16.225(4) Δ Me2CO/H2O c = 18.371(5) * III II PIMYUF 1998 [Co (bipy)3][Co 2(ox)3]ClO4 P4132 a = 15.287(2) Λ S.D. H2O

Gel S.D. H2O using * II III DAXXIJ 1999 [Ru (bipy)3][LiCr (ox)3]·H2O P213 a = 15.289(2) Λ enantiomerically pure 2+ [Ru(bipy)3]

Gel S.D. H2O using * II III DAXZIL 1999 [Ru (bipy)3][LiCr (ox)3]·H2O P213 a = 15.293(8) Δ enantiomerically pure 2+ [Ru(bipy)3]

Gel S.D. H2O using * II III DAYBAG 1999 [Ni (bipy)3][LiCr (ox)3]·H2O P213 a = 15.380(5) Δ enantiomerically pure 3- [Cr(ox)3] † 1999 [RuII(bipy) ][NaRuIII(ox) ] P2 3 a = 15.556(1) Λ GOLRII 3 3 1 Gel S.D. H2O GOLROO* 1999 [RuII(bipy) ][NaRhIII(ox) ] P2 3 a = 15.515(2) Δ 3 3 1 Gel S.D. H2O GOLRUU* 1999 [RuII(bipy) ][NaAlIII(ox) ] P2 3 a = 15.407(4) Δ 3 3 1 Gel S.D. H2O CUFQOJ* 2000 [ZnII(bipy) ][NaCrIII(ox) ] P2 3 a = 15.637(1) Δ 3 3 1 Gel S.D. H2O CUFROK* 2000 [CoII(bipy) ][NaCrIII(ox) ] P2 3 a = 15.585(0) Λ 3 3 1 Gel S.D. H2O CUFRUQ‡ 2000 [RuII(bipy) ][LiCrIII(ox) ] P2 3 a = 15.309(0) Λ 3 3 1 Gel S.D. H2O CUFSAX§ 2000 [CoII(bipy) ][LiCrIII(ox) ] P2 3 a = 15.309(1) Δ 3 3 1 Gel S.D. H2O

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CUFSAX01* 2000 [CoII(bipy) ][LiCrIII(ox) ] P2 3 a = 15.387(0) Λ 3 3 1 Gel S.D. H2O * II II III GUNFAW 2001 [Ru (bipy)3][Mn Cr (ox)3]ClO4 P4132 a = 15.506(2) Λ S.D. MeOH

Gel S.D. H2O using ** II II III GUNFAW01 2001 [Ru (bipy)3][Mn Cr (ox)3]ClO4 P213 a = 15.490(1) Δ enantiomerically pure 2+ [Ru(bipy)3] II II AXAFIO†† 2004 [Ru (bipy)3][Cu 2(ox)3] P4132 a = 15.297(0) Λ Gel S.D. H2O Solvothermal (150ºC) ‡‡ II III CEHYUK 2006 [Mo (phen)3][NaMo (ox)3] P213 a = 16.116(0) Λ MeOH/H2O

Gel S.D. H2O using §§ II II GENCAE 2006 [Ru (bipy)3][Mn 2(ox)3] P4332 a = 15.492(2) Δ enantiomerically pure 2+ [Ru(bipy)3]

Gel S.D. H2O using §§ II II GEPTUR 2006 [Ru (bipy)3][Mn 2(ox)3] P4132 a = 15.507(1) Λ enantiomerically pure 2+ [Ru(bipy)3] MeCN/MeOH (N , II II 2(g) HISSEI*** 2007 [Co (bipy)3][Co 2(ox)3] P4332 a = 15.387(0) Δ 5ºC) Solvothermal (150ºC) ‡‡ II III MIKJEW 2007 [Fe (phen)3][NaFe (ox)3] P213 a = 16.109(1) Λ MeOH/H2O a = 10.436(2)

*** FEJNIS II III b = 29.919(6) 2008 [Fe (phen)3][NaFe (ox)3]·4H2O P21/c Δ S.D. EtOH/H2O c = 14.883(3) β = 99.47(3) II III XAHZUD*** 2010 [Ru (bipy)3][NaCr (ox)3] P213 a = 15.510(0) Δ S.E. H2O (5ºC) Structure measured at * 295 K, † 193 K, ‡ 100 K, § 10 K, ** 160 K, †† 183 K, ‡‡ 273 K, §§ 253 K, *** 293 K

Given the information presented in Table 19, it is noteworthy that most of the crystals grown at room temperature from water alone resulted from a diffusion through a medium of silica gel impregnated with oxalic acid and/or sodium oxalate. This crystallisation method is very time consuming (weeks-months) but is preferred by many authors as it prevents the rapid precipitation of a microcrystalline product by slowing the diffusion of the aqueous solution into the gel and the in situ formation of the oxalato complex. The slowing of both of these processes impedes the formation of the metal-organic framework thus producing high quality crystals. Of II 2+ particular interest are the crystallisation methods where [M (phen)3] acts as the

guest complex counterion to yield the cubic P213 structure. All of these experiments mixtures of water and a high vapour pressure solvent such as acetone at either elevated or depressed temperatures. Using the data available in the CSD, the unit

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II I III cells of these cubic P213 [M (phen)3][M M (ox)3] structures are calculated to be ca. 500 Å3 larger than their 2,2′-bipyridine analogues yet still maintain the same crystal packing.

A B A B Metal dilution experiments (M xM 1-x, where M and M share the same oxidation II I III II number) for compounds of the type [M (L)3][M M (ox)3] can occur at the M site A B I III III giving the general formula [M xM 1-x(L)3][M M (ox)3] or at the M site giving the II I A B general formula [M (L)3][M M xM 1-x(ox)3]. The former system is described as a cationic metal complex dilution, while the latter is an anionic metal complex dilution. Figure 72 shows the crystal packing along the a axis that is typical for II I III cubic structures with the general formula [M (L)3][M M (ox)3]. The cationic 2+ 2- [Ru(bipy)3] guests are shown in black while the anionic {[NaCr(ox)3] }n framework is shown in red; this structure has the formula Δ-[Ru(bipy)3][NaCr(ox)3] (CSD reference code XAHZUD).65

Figure 72: [100] projection of Δ-[Ru(bipy)3][NaCr(ox)3] reported for the 2010 structure by Hauser et al. (XAHZUD) showing the crystal packing common to the P213 cubic structures listed in Table 19. 2+ 2- The cationic [Ru(bipy)3] guests are shown in black while the anionic {[NaCr(ox)3] }n framework is shown in red.65

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Throughout this project, several co-crystalline coordination frameworks of these types were synthesised following a modified literature procedure involving II 2+ II III 3- [M (L)3] (M = Ni, Ru; L = 2,2′-bipyridine, 1,10-phenanthroline) and [M (ox)3] (MIII = Cr, Fe). Co-crystallisation experiments were designed so that metal dilutions of either the cationic and anionic metal complexes could be examined. Table 20 summarises the co-crystallisation experiments that will be discussed within this section and highlights all of the metal complexes involved, their relative solution state concentrations (xsolution) and the formulae of the resulting solid state co-crystalline coordination frameworks. The sodium chloride solution (0.02 M) was used as a source of Na+ ions; all metal complexes shown in Table 20 are soluble in water. The different types of experiments were conducted in triplicate to test reproducibility and on a small scale (ca. 10 mg).* In addition to the 18 batches, some co-crystallisations were repeated under different conditions in order to further understand the results obtained from the triplicate experiments. The co-crystallisation systems in Table 20 are numbered 1 to 6. These numbers will be used throughout to simplify the discussion of the various results.

* A small scale was chosen to ensure a representative sample of crystals was analysed using the ca. 10 crystals that were harvested i.e. a greater proportion of the crystals that were formed during crystallisation.

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Table 20: Summary of co-crystallisation experiments showing all metal complexes involved and the formula for the resulting solid state co-crystalline metal-organic framework.

Aqueous state (in the presence of 0.02 M NaCl) Solid state

Co-crystallisation 0.005 M 0.005 M 0.01 M system type Complex A Complex B Counterion Co-crystal formula (at least 3 xsolution = 0.50 xsolution = 0.50 complex replicates) II 2+ III 3- Homoleptic system: Co-crystallisation of [M (bipy)3] with [M (ox)3] 1 [Ni(bipy)3]Cl2 [Ru(bipy)3]Cl2 K3[Cr(ox)3] [NixRu1-x(bipy)3][NaCr(ox)3] 2 K3[Cr(ox)3] K3[Fe(ox)3] [Ru(bipy)3]Cl2 [Ru(bipy)3][NaCrxFe1-x(ox)3]

II 2+ III 3- Homoleptic system: Co-crystallisation of [M (phen)3] with [M (ox)3]

3 [Ni(phen)3]Cl2 [Ru(phen)3]Cl2 K3[Cr(ox)3] unknown

4 K3[Cr(ox)3] K3[Fe(ox)3] [Ru(phen)3]Cl2 unknown

II 2+ Different ligand system: Co-crystallisation of [M (L)3] (L = bipy, phen) with III 3- [M (ox)3] 5 [Ni(bipy)3]Cl2 [Ru(phen)3]Cl2 K3[Cr(ox)3] [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] 6 [Ni(phen)3]Cl2 [Ru(bipy)3]Cl2 K3[Cr(ox)3] [Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3]

The different systems of experiments shown in Table 20 are grouped according to the II 2+ II 2+ type of cationic metal complex involved ([M (bipy)3] and/or [M (phen)3] ). The first four types of experiments are classified as homoleptic systems i.e. the complexes involved in the dilution have the same ligands. The last two experiments summarised in Table 20 describe different ligand systems involving the II 2+ II 2+ co-crystallisation of [M (bipy)3] and [M (phen)3] . The term different ligand is used within this context to describe systems where the metal centres of two or more metal complexes, each with different types of ligands, share partial occupancy of the same crystallographic site.

Due to the kinetic inertness of Ru2+ polypyridyl and Cr3+ complexes (with respect to ligand exchange), any chromium and ruthenium SEM-EDX elemental values are considered to be representative of their corresponding metal complexes. To avoid 3- any possibility of ligand exchange, combinations involving both [Fe(ox)3] and

2+ 59,60 [Ni(L)3] were avoided due to the labile nature of iron and nickel complexes. Therefore, any SEM-EDX elemental data obtained for iron and nickel were treated in

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CHAPTER 5 the same way as the data obtained for chromium and ruthenium. This is because although ligand exchange occurs, only one free bidentate ligand species is present in solution and the formation of the chelated complex is thermodynamically favoured due to the chelate effect. The products were characterised by SEM-EDX and where possible by SCXRD and PXRD. Values such as MII:MIII ratios (where the MIII is normalised to 1) and xsolid are reported as xˉ ± s (xˉ = sample mean; s = sample standard deviation). Microscope images of representative co-crystals from systems 1, 3 and 5 are shown in Figure 73. For exact preparative experimental details, refer to Section 3.3.7.

(a) (b) (c)

100 µm 100 µm 100 µm

Figure 73: (a) Single co-crystals of the general formula [NixRu1-x(bipy)3][NaCr(ox)3] resulting from 2+ 2+ 3- the co-crystallisation of a 1:1:2 ratio of [Ni(bipy)3] , [Ru(bipy)3] and [Cr(ox)3] in the presence of NaCl (system 1), (b) single co-crystal resulting from the co-crystallisation of a 1:1:2 ratio of 2+ 2+ 3- [Ni(phen)3] , [Ru(phen)3] and [Cr(ox)3] in the presence of NaCl (system 3) and (c) a single co-crystal of the general formula [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] resulting from the 2+ 2+ 3- co-crystallisation of a 1:1:2 ratio of [Ni(bipy)3] , [Ruphen)3] and [Cr(ox)3] in the presence of II 2+ NaCl (system 5). All co-crystals grown from solutions containing [M (bipy)3] had tetrahedral habits II 2+ while those that did not involve [M (bipy)3] (systems 3 and 4) had rectangular prism habits. It is noteworthy that the rectangular prism co-crystals crumbled shortly after removal from the mother liquor as can be seen in (b); the tetrahedra appeared to uphold their structural integrity after removal from solution. Regardless of the system, all of the experiments produced only red co-crystals.

Representative SEM-EDX statistical data for these systems are summarised in Table 21 and show the mean (xˉ), standard deviation (s) and minimum (Min) and maximum (Max) values for n crystals. The data in each row, determined by EDX, correspond to the element highlighted in coloured text (either Ni or Cr). For example, the statistics for the system in the first row relate to the nickel mole fraction relative to ruthenium in the solid state, whereas the values in the second row relate to the chromium content relative to iron. The formula for all co-crystals except those from experiment types 3 and 4 (shaded cells) are included in the table. Structural information was not collected for co-crystals resulting from experiment types 3 and 4 (shaded cells) due to their structural instability once removed from the mother liquor and hence the

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CHAPTER 5 formula for these co-crystals is not known. The results relating to each system will be discussed in detail in the relevant sections within this chapter.

Table 21: Statistical summary of xsolid values obtained from EDX data for experiments 1-6 shown in Table 20. The sample mean (xˉ), standard deviation (s), the number of co-crystals analysed (n), the minimum and maximum xsolid values are shown along with the co-crystal formula (where known). The xsolid data correspond to the highlighted element (blue or red). Structural information was not collected for co-crystals resulting from experiment types 3 and 4 (shaded cells) and hence the formula for these co-crystals is not known.

Experiment Co-crystal formula (where known) xˉ(xsolid) s(xsolid) n Min Max number 1 [NixRu1-x(bipy)3][NaCr(ox)3] 0.47 0.02 11 0.43 0.52 2 [Ru(bipy)3][NaCrxFe1-x(ox)3] 0.58 0.01 8 0.57 0.60 2+ 2+ 3 Cations: [ Ni(phen)3] , [Ru(phen)3] 3- Anion: [Cr(ox)3] 0.51 0.02 11 0.47 0.55 2+ 4 Cation: [Ru(phen)3] 3- 3- Anions: [Cr(ox)3] , [Fe(ox)3] 0.44 0.02 10 0.38 0.47 5 [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] 0.77 0.02 9 0.74 0.80 6 [Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3] 0.21 0.02 12 0.18 0.23

Figure 74 is a colour-coded graphical representation of the same EDX information summarised in Table 21. The x axis shows the experiment number (according to the numbering in Table 20) and the metal ratio of interest, either Ni:Ru or Cr:Fe. The y axes are colour-coded so that the blue axis on the left and red axis on the right correspond to the atomic fraction of Ni or Cr respectively (xsolid). The data points are also colour-coded to show axis association and represent the mean xsolid value found for a particular system. The general formula (where found) is situated near each respective data point. The error bars extend to one standard deviation in either direction and as such, are different for each system shown. For example, the data for 2+ 2+ the system resulting in the co-crystallisation of [Ni(bipy)3] , [Ru(bipy)3] and 3- [Cr(ox)3] in the presence of NaCl (experiment type 1) are represented by the point labelled [NixRu1-x(bipy)3][NaCr(ox)3]. Similarly, the data for co-crystals resulting from experiment type 2 are labelled [Ru(bipy)3][NaCrxFe1-x(ox)3]. Co-crystals from II 2+ experiment types 3 and 4, where [M (phen)3] was the only cationic complex in solution were unstable when removed from the mother liquor. The data points for these two systems are enclosed in the black rectangle. Structural information via

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X-ray diffraction was not collected for these systems as the crystals diffracted very poorly. Therefore, the formula for these co-crystals is unknown.

EDX GRAPHICAL SUMMARY 0.90 0.90

[Ni(bipy) ] [Ru(phen) ] [NaCr(ox) ] 0.80 3 x 3 1-x 3 0.80

0.70 0.70

[Ru(bipy)3][NaCrx Fe1-x (ox)3]

0.60 0.60

solid

solid

x x 0.50 0.50

[Ni Ru (bipy) ][NaCr(ox) ]

0.40 x 1-x 3 3 0.40

Average Ni Ni Average Average Cr Average

0.30 0.30 [Ni(phen)3]x [Ru(bipy)3]1-x [NaCr(ox)3]

0.20 0.20

0.10 0.10 0 11 22 33 44 55 66 7 Ni:Ru Cr:Fe Ni:Ru Cr:Fe Ni:Ru Ni:Ru Experiment system (M:M ratio)

Figure 74: EDX plot showing the metal ratio of interest (Ni:Ru or Cr:Fe) and experiment system on the x axis against the xsolid of Ni or Cr on the left and right y axes respectively. The data points represent the average xsolid values for either Ni or Cr deduced from both surface and crushed co-crystal measurements, while the error bars correspond to one standard deviation. The general formula (where known) is shown near the data point for the corresponding system. Co-crystals from experiment types II 2+ 3 and 4, where [M (phen)3] was the only cationic complex in solution diffracted very poorly. The data points for these two systems are enclosed in the black rectangle; their formula in unknown. The plot is colour-coded so that all features in blue correspond to the left axis, while the features in red correspond to the right axis.

It is important to note that representing the statistics for all the transition metals involved in each dilution (Ni and Ru or Cr and Fe) would be redundant since the raw EDX data relating to their concentrations are interpreted as ratios (Ni:Ru and Fe:Cr) rather than as absolute values. Due to the binary nature of the dilutions, the ratios sum up to one and therefore only one set of statistics and by extension, one axis is needed per experiment batch.

Where possible, co-crystals were also characterised using single crystal and powder X-Ray diffraction techniques. Table 22 summarises the crystal and refinement data for [Ni0.50Ru0.50(bipy)3][NaCr(ox)3], [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] and

[Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] co-crystals. A SCXRD full dataset for the compound [Ru(bipy)3][NaCrxFe1-x(ox)3] (system 2) was not collected as positional

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CHAPTER 5 occupancy is an inaccurate indicator of the relative concentration of complexes

(i.e. xsolid) for atoms with similar electron density, such as with chromium and iron. The attached CD contains the crystallographic information files (.cif) for these crystal structures. Unlike SCXRD, PXRD is a bulk analysis technique and can be used instead of, or in addition to, SCXRD to further understand the structural properties of crystalline material. In lieu of SCXRD data, structural information for co-crystals of the type [Ru(bipy)3][NaCrxFe1-x(ox)3] was ascertained using PXRD by comparing the powder pattern with patterns simulated from SCXRD data of the other systems. Powder patterns were also collected for [NixRu1-x(bipy)3][NaCr(ox)3],

[Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] and [Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3] co-crystals.

Figure 75 shows the PXRD patterns of co-crystals indexed against a pattern simulated from SCXRD data collected from a [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] single co-crystal. The similarity between all of the experimental patterns shown in Figure 75 indicate that the co-crystals from these experiments form isomorphous structures. There are no additional peaks observed for the experimental patterns when compared to the simulated trace. This is a strong indicator that all of the co-crystals form with the same structure i.e. no evidence of phase impurities. Detailed X-Ray data for the various systems are discussed in the corresponding sections within this chapter.

2+ 2+ Co-crystals resulting from solutions containing [Ni(phen)3] , [Ru(phen)3] and 3- 2+ 3- [Cr(ox)3] (system 3) and solutions containing [Ru(phen)3] , [Cr(ox)3] and 3- [Fe(ox)3] (system 4) diffracted poorly. This was due to physical deterioration likely caused by dehydration when the co-crystals were removed from the mother liquor.365 Consequently, diffraction data for co-crystals resulting from these systems were not collected.

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Table 22: Summary of crystal and refinement data for structures of [Ni0.50Ru0.50(bipy)3][NaCr(ox)3], [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] and [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3]. Appendix F contains a summary of parameters such as bond lengths and bond angles. The accompanying CD contains the crystallographic information files (.cif) for these crystal structures.

w ] 3 where where

1/2 [NaCr(ox) 0.80 ]} 2 ) 0.80 Ru 2 ] c 3 12 F O ( w [ 0.20

 ]/ 2 ) [Ru(bipy)

2 NaNi c

6

F 0.20

]

– 3 905

CrN 2 (12) o

24 7 , 0

) , 0. F

H 5 (

 37 (

12

3 w K (phen) 575 8 79 1 [ 1025 37.20 ed 2 20  Ni 0.3 [ C 914.61 173(2) Mo Cubic P 15.4642(3) 3698.1 1.644 4 R Tetrahedron 0.250.25 × × 0.25 0.808 0.95316,1 2169(0.0318) 1870 2 0.04 0. 0.0 0.0 1.0 - = {

] 3 (all) 2 wR

) and [NaCr(ox) 0.20 o F 0.20 Ru ( ] 3  12 O > 2

0.80 o

F

[Ru(phen) NaNi

6 | | for

o ) 0.80

F ] 5 | 530 3 CrN  (1

24

||/

, 0. c

68 H 7

 F 81 85 0 , (4) |

3 K

(bipy) 4 5 37 1 – 37.20 2

| Ni 0.31 o [ C 889.18 173(2) Mo Cubic P 15.4664(4) 3699. 1.597 4 Red Tetrahedron 0.230.23 × × 0.23 0.868 0.83648,1 2287(0.0473) 1458 216 0.04 0.09 0.0 0.0 1.0 - F || 

] 3

1 = 0.50 R Ru 12

O ][NaCr(ox)

)/3. 3 2 0.50 c F

(bipy) NaNi + 2

6 70

2 o (16) 0.50 1

F

CrN

, 0.4 Ru

, 0 24 = (



07 38 7 (3)

50

3 K 0.50 H 4 074 P 1 2 )] considered observed. 36 2

I ], ], Ni 0.3 ( [ C 887.49 173(2) Mo Cubic P 15.4998 3723.73(7) 1.583 4 Red Tetrahedron 0.190.19 × × 0.19 0.831 0.90114,1 2238(0.0278) 1771 17 0.03 0.05 0.01 0.0 1.0 - P  B + > 2

2 I )

P

] A ]

)) 3 1 - - I (

Å



- ) + (

] 2 ] 1

o 3 [mm - [e -

) > 2 F )

(

 I int

2 ( K

]

R a  3

-

(

s 2 [g cm[g min,max a [g [g mol

[Å [K] [Å] c var ind ob 1  (Mo min,max Reflections with [

Formula M T Radiation Crystal System Space Group a V D Z Colour Habit Dimensions [mm]  T N N N R wR B A, parameterFlack GoF  a = 1/[ Dhjajuhtajtajtr

168 Dgfshfdhgdjaj

CHAPTER 5

II III PXRD: [M (L)3][NaM (ox)3] frameworks Simulated from SCXRD of 210 [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] 25000 (P213) 400 111 211 411 221

20000 [NixRu1-x(bipy)3][NaCr(ox)3]

15000

[Ru(bipy)3][NaCrxFe1-x(ox)3] Counts 10000 [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3]

5000 [Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3]

0 5 10 15 20 25 30 5 10 15 20 25 30 Position [ 2θ (Cu)]

Figure 75: PXRD patterns of co-crystals from systems 1, 2, 5, 6 (reading down) that were collected at room temperature indexed against a simulated powder pattern collected from a [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] single co-crystal at 173K.

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CHAPTER 5

5.2.3 [NixRu1-x(bipy)3][NaCr(ox)3] (system 1)

Crystalline material was first observed four days after the initial mixing of the various aqueous solutions listed in Table 20. Co-crystallisation was stopped at two weeks after mixing, at which time the mother liquor was observed to be slightly 2+ tinged with red, likely due to free [Ru(bipy)3] in solution. These observations were consistent for all of the replicate experiments attempted.

It is sometimes possible in systems where the pure compounds differ in colour or habit to qualitatively assess the success or failure of co-crystallisation through simple observation. The pure compound [Ru(bipy)3][NaCr(ox)3] crystallises as deep red tetrahedra, while the nickel analogue, [Ni(bipy)3][NaCr(ox)3] crystallises as dichroic pink/purple tetrahedra depending on the angle of view. The co-crystallisation of 2+ 2+ 3- [Ni(bipy)3] with [Ru(bipy)3] in the presence of [Cr(ox)3] and NaCl produced dark pink tetrahedral crystals of the formula [NixRu1-x(bipy)3][NaCr(ox)3]. Due to the colour similarity between the co-crystals and the crystals of the pure compounds, visual inspection was not a reliable screening technique to assess the success of co-crystallisation. However, it is noteworthy that all of the co-crystals were red indicating that no [Ni(bipy)3][NaCr(ox)3] crystals had formed.

The first attempt at synthesising these co-crystals produced a complicated and intertwined mass of crystalline material. Figure 76 shows an SEM image taken of the microcrystalline material formed from this first attempt.

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Figure 76: SEM image of intertwined mass of crystalline [NixRu1-x(bipy)3][NaCr(ox)3] co-crystals (system 1). The areas outlined in red were analysed at close range due to their acceptable angle with respect to the X-Ray beam.

Even though the crystals shown in Figure 76 were not single and most had an undesirable orientation with respect to the X-ray beam, EDX analysis was carried out on a few selected areas (outlined in red). Ideally, single crystal EDX spectra at high magnification are measured on flat and smooth surfaces that are perpendicular to the X-ray beam. Furthermore, analysis should be conducted on single crystals that have well-defined edges. The surface angle with respect to the X-ray beam and the surface topography influence the quantitative results from samples involving elements that have spectral lines at low energy (< 4 keV) such as ruthenium (Lα and Lβ at 2.6 and 2.7 keV) (see Appendix A).

Therefore, due to the undesirable formation of these crystals, none of the EDX results could be regarded as single crystal values. Regardless of their form, EDX analysis of this sample was used to gather information regarding the composition of the bulk material. Analysis at both close range and low magnification (bulk analysis) yielded an average Ni:Ru ratio of ca. 0.50:0.50. Due to the quality of the co-crystals obtained, this batch was not considered as part of the single crystal analysis for this system but rather as a cursory test experiment. To encourage the formation of single crystals, the vials containing the co-crystallising solutions for subsequent experiments were allowed to stand completely undisturbed throughout the experiment. Experiments for this particular system were repeated an additional time

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CHAPTER 5 giving a total of four attempts, the last three of which produced single crystals with well-defined edges and smooth surfaces. An SEM image of a single

[NixRu1-x(bipy)3][NaCr(ox)3] co-crystal is shown in Figure 77. The co-crystal in this image is shown to be mounted upright to highlight the tetrahedral habit, however in subsequent SEM-EDX sessions, co-crystals were mounted as inverted tetrahedra so that a flat surface could be analysed.

Figure 77: SEM image of a representative [NixRu1-x(bipy)3][NaCr(ox)3] single co-crystal resulting 2+ 2+ 3- from the co-crystallisation of a 1:1:2 ratio of [Ni(bipy)3] , [Ru(bipy)3] and [Cr(ox)3] in the presence of NaCl (system 1). Most single co-crystals were found to have edges between 150-250 m in length. The tetrahedra were observed to maintain their structural integrity under the vacuum, exhibiting well-defined edges and smooth surfaces for the entire duration of the SEM-EDX session.

A representative EDX spectrum measured from a single co-crystal resulting from the 2+ 2+ 3- co-crystallisation of a 1:1:2 ratio of [Ni(bipy)3] , [Ru(bipy)3] and [Cr(ox)3] in the presence of NaCl (system 1) is shown in Figure 78. The raw atomic percentages (At%) of the transition metals and their relative ratios are also shown. The co-crystal from which this EDX spectrum was obtained was harvested from the same solution as the co-crystal shown in Figure 77.

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Formula

[Ni0.49Ru0.51(bipy)3][NaCr(ox)3]

Raw At% Solid Ratio (Cr) 2.13 1 (Ni) 1.07 0.50 (Ru) 1.11 0.50

Figure 78: EDX spectrum from a tetrahedral crystal with the formula [Ni0.49Ru0.51(bipy)3][NaCr(ox)3]. The blue shaded area highlights the presence of the Na Kα line at 1.1 keV. Quantitative EDX data for the transition metals are shown as raw atomic percentages (At%).

The spectrum shown in Figure 78 exhibits peaks belonging to chromium (5.4 keV), nickel (7.5 keV) and ruthenium (2.6 keV), indicating the presence of each respective metal complex. The spectrum also shows nitrogen and oxygen peaks at 0.4 and 0.5 keV and a large carbon peak at 0.3 keV; the former two are attributed to the ligands while the latter is caused by the carbon content in the ligands and in the carbon-coating. A sodium peak at 1.1 keV is also observed.* Chlorine and potassium peaks, which if present would occur at 2.6 and 3.3 keV respectively, are not observed. The absence of potassium and chlorine peaks indicates that both K+ and Cl- ions are left behind in the mother liquor. EDX spectra of the powder residues resulting from the evaporated mother liquor show large peaks for both potassium and chlorine (see Appendix B).

The quantitative EDX data reveal a Ni:Ru:Cr ratio of 1:1:2, which is consistent with the ratio of the starting solution. Subsequent measurements from the same co-crystal support this stoichiometry. The co-crystal represented by this EDX spectrum was one of eleven co-crystals analysed from this batch (24 measurements). All spectral characteristics discussed in relation to the spectrum in Figure 78 are applicable to the spectra of the other co-crystals analysed from this batch and subsequent replicate batches. This also applies to the quantitative EDX data as of all of the co-crystals

*The At% calculated for sodium is unreliable as the peak occurs at low energy and hence is influenced by changes in the surface tilt with respect to the X-ray beam.

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CHAPTER 5 yielded very similar results. The average (Ni+Ru):Cr ratio of single crystals for the batch was consistently found to be 1:1 ((1.03 ± 0.03):1). Similarly, the mean nickel xsolid value was calculated to be 0.47 ± 0.02 giving an average single crystal formula of [Ni0.47Ru0.53(bipy)3][NaCr(ox)3]. The minimum and maximum nickel xsolid values were found to be within two standard deviations of the mean at 0.43 and 0.52 respectively (refer to Table 21). The statistics for this system suggest that xsolid ≈ xsolution with minimal to no supramolecular selection involved during the synthesis of these co-crystals. This is in contrast to the previously studied

[NixRu1-x(bipy)3](PF6)2 molecular system, which was shown to display supramolecular selection as indicated by the larger standard deviation (0.51 ± 0.09).35,261

Since EDX is a surface technique, compositional homogeneity was examined by measuring the EDX of a selection of crushed single co-crystals. The mean

(Ni+Ru):Cr ratio and nickel xsolid value for crushed single co-crystals were calculated to be (1.00 ± 0.03):1 and 0.47 ± 0.02. These results are consistent with surface measurements suggesting that co-crystals synthesised under these conditions, do so without forming a concentration gradient. Due to the direct overlap of chlorine and ruthenium peaks, the nickel xsolid values obtained from the solid residue resulting from evaporating the solvent from the mother liquor are unreliable; however they do suggest a final solution composition containing a 1:1 Ni:Ru ratio (0.54 ± 0.04). Therefore, the results indicate that the composition of these co-crystals is largly dependent on the composition of the solution and that the Ni:Ru ratio in solution remains relatively unchanged, such that xsolution = xsolid at any point during co-crystallisation.

II 2+ It is interesting that [M (bipy)3] complexes displayed significant supramolecular selection during co-crystallisations that formed [NixRu1-x(bipy)3](PF6)2 co-crystals, yet supramolecular selection for [NixRu1-x(bipy)3][NaCr(ox)3] co-crystals seems to be almost negligible. A detailed discussion regarding the X-ray crystal structures for

[NixRu1-x(bipy)3](PF6)2 co-crystals has been published from research that was done

35 II 2+ previously by the candidate. It was found that pairs of [M (bipy)3] complexes in

[NixRu1-x(bipy)3](PF6)2 interact through a set of six EF π-interactions in much the II same way as for pure [M (bipy)3](PF6)2 complexes. No such π-interactions are

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II 2+ present between neighbouring [M (bipy)3] complexes in any of the II II 2+ [M (bipy)3][NaCr(ox)3] structures listed in Table 19. Instead, [M (bipy)3] complexes in these structures occupy cavities formed by the anionic 3D polymeric framework. X-ray diffraction data were collected for [NixRu1-x(bipy)3][NaCr(ox)3] co-crystals in order to better comprehend the structural aspects of co-crystallisation.

Single crystal refinement data for the [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] co-crystal are provided in Table 22. A simulated pattern calculated from the single crystal data is shown in Figure 75 and was used to index the experimental powder patterns shown.

The topology exhibited for the [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] co-crystal shows a 2- chiral 3D arrangement where the formal [NaCr(ox)3] units represent three connecting nodes to form a 3-connected 10-gon (10, 3) framework. The structure for this compound belongs to P213 space group and is isomorphous to the cubic structures listed in Table 19. The unit cell parameters (a = 15.49981(16) Å, V = 3723.73(7) Å3) are very similar to the parameters of the various pure structures listed in Table 19 indicating that the dilution of the MII site does not greatly influence the crystal packing.

2- + There is a third of a formal [NaCr(ox)3] unit i.e. one oxalato ligand bridging a Na 3+ II 2+ and Cr ion and a third of a [M (bipy)3] molecule in the asymmetric unit. The II 2+ position of the metal centres in the [M (bipy)3] molecule were modelled as a disordered mixture of Ni and Ru and their relative occupancies were refined (with fixed and equivalent displacement parameters) to be 0.47 Ni and 0.53 Ru. These values are in very close agreement to those obtained by SEM-EDX results, which showed that co-crystals of this type, formed from a solution containing an equimolar 2+ 2+ ratio of [Ni(bipy)3] and [Ru(bipy)3] do so with nickel xsolid values close to 0.50. When the relative occupancies were fixed at Ni 0.40 or Ni 0.60 prior to refinement, only very minimal changes in the refinement residuals were observed. Therefore, despite the electron density difference between Ni and Ru, simple refinement of positional occupancy is not as reliable as the SEM-EDX technique to ascertain the nickel xsolid concentration in these materials. Hence, the final refinement cycles were conducted with the relative occupancies fixed at 0.50.

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Each oxalato ligand bridges adjacent Na+ and Cr3+ ions in all three dimensions resulting in a polymeric net consisting of connected helical strands (three connected II 2+ at each node). The [M (bipy)3] cations are located within the voids produced by the 2- 2- II 2+ polymeric [NaCr(ox)3] framework. Every [NaCr(ox)3] subunit and [M (bipy)3] molecule exhibits the same Δ-configuration. Spontaneous resolution during the preparation of these types of materials when starting from racemic mixtures (such as in this case) has been observed in previously reported structures due to the II 2+ templating effect of [M (bipy)3] . Some published structures report the presence of II 2+ water situated within cavities formed by three adjacent [M (bipy)3] molecules; no water was found within this structure despite containing a sufficient void volume of 314.5 Å3.

A comparison of the structures listed in Table 19 shows that the mean MII-N bond 2+ lengths for [Ni(bipy)3] guests are slightly longer at 2.088 Å than those for 2+ II [Ru(bipy)3] guests (2.057 Å). The mean M -N bond length found here, refined to 2.071(2) Å, approximately half-way between these two values. This length is slightly

35 longer than that found for the [NixRu1-x(bipy)3](PF6)2 system (2.066(2) Å). The angle subtended at the MII site by the 2,2′-bipyridine ligand (bite angle) is 78.66(9)°. Unlike the MII-N bond length, the bite angles for both complex species are very similar; the angles for both types of complexes that are present in published structures are clustered within a 1° range (78.39-79.39°). The distance between Ni/Ru sites of neighbouring complexes was found to be 9.492 Å.

The mean Cr-O bond length present in this framework is refined to 1.968(2) Å, while the average Na-O length is longer at 2.333(2) Å. These values are consistent with bond lengths found for previously reported structures (Table 19) containing the 2- [NaCr(ox)3] unit (average Cr-O = 1.965 Å, average Na-O = 2.336 Å). The O-Cr-O bite angle is 83.50(8)°, while the angle subtended at the Na site is 74.11(7)°; accounting for the uncertainty in the last decimal place, both values fall within the ranges observed for literature compounds (83.27- 83.82 for O-Cr-O and 72.55-74.08 for O-Na-O). The [100] projections showing the host anionic net and the II 2+ [M (bipy)3] guests are shown in Figure 79.

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2- 2+ Figure 79: [100] projection of {Δ-[NaCr(ox)3] }n (left) and Δ-[Ni0.50Ru0.50(bipy)3] (right) for the Δ-[Ni0.50Ru0.50(bipy)3][NaCr(ox)3] compound.

2- II 2+ Both the formal [NaCr(ox)3] units and the [M (bipy)3] cations possess D3 point symmetry. A perfectly octahedral tris-bidentate complex, when viewed along its C3 axis, displays two perfectly staggered equilateral triangles (twist angle, Φ = 60°) of sides s separated by a distance h (h = (2/3)1/2 s).* An s/h ratio greater than 1.22 describes a compressed octahedral geometry while those that are lower describe elongated complexes (see Figure 80).366 The geometry around each metallic site for the cubic structures listed in Table 19 can be described as trigonally distorted and compressed octahedra; the MI sites are observed to exhibit the greatest distortion. Φ = 60° O O O 90° M ≡ h O O O s

Figure 80: Diagram highlighting how one donor atom from each ligand is used to create the triangular faces from, which the centroids are calculated in a tris-bidentate octahedral metal complex (far left). The relationship between the two faces, defined by the twist angle, Φ is shown in the central schematic; while the s and h parameters for regular octahedra are shown on the far right.

*The twist angle (Φ), is calculated by first creating centroids using donor oxygen (oxalato ligand) or nitrogen (2,2′-bipyridine ligand) atoms from opposite triangular faces of the octahedron. The twist is defined as the torsion angle between donor atoms from the same ligand through the centroids. The length of the side (s) is the average distance between adjacent donor atoms from the same triangular face while the height (h) is taken as the distance between the centroids.

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2+ The [Ni0.50Ru0.50(bipy)3] guest complex in [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] may be described by a twist angle of 49.69° and an s/h ratio of 1.41 (s = 3.058 Å (mean value), h = 2.165 Å). These values correspond to a trigonally twisted and compressed octahedron. Despite the shared occupancy of the metal centre within the II 2+ II guest [M (bipy)3] complex, all geometric attributes bar the mean M -N bond II 2+ length are comparable to [M (bipy)3] guests in the cubic frameworks shown in Table 19 (MII = Ni, Ru).

3+ + 2- The Cr and Na environments in the [NaCr(ox)3] fragment possess twist angles of 53.24° and 45.83° respectively. Both complex fragments can be described as compressed octahedra with s/h ratios of 1.31 for the chromium-centred complex and 1.50 for the Na+. These twist angles and s/h ratios indicate a greater twist and compression distortion at the sodium-centred fragment than that present at the 2- chromium counterpart. All parameters regarding the [NaCr(ox)3] polymeric net are congruent with those for literature structures. A summary of bond lengths and angles are provided in Appendix F.

The experimental powder pattern of [NixRu1-x(bipy)3][NaCr(ox)3] is shown in Figure 75 (red trace) directly below the simulated pattern generated from the single crystal data. The positions and relative intensities of peaks in the experimental pattern agree well with the profile of the simulated trace. Firstly, this indicates that the single crystal simulation is representative of the bulk phase and that only one phase is present in the bulk sample. The similarities in the relative intensities of peaks between the two patterns also signify that preferred orientation, which is a common issue for highly crystalline samples prepared as thin films such as this one is not a factor here. Furthermore, the similarity of the powder pattern to the simulation indicates that the phase and unit cell dimensions remain relatively constant between room temperature and 173 K.

Qualitatively, the peaks in the experimental pattern appear to be narrow. The full width at half maximum (FWHM) of the peaks do not appear to be significantly large with values between 0.0836 and 0.1171°2θ. For example, the [210] reflection at around 12.8°2θ, which is the most intense peak in this pattern has a FWHM of 0.1004°2θ.

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This is interesting because peak broadening has been observed for systems that

35,261 displayed supramolecular selection such as [NixRu1-x(bipy)3](PF6)2. It was found that [Ni(bipy)3](PF6)2 single crystals had slightly larger unit cells than

[Ru(bipy)3](PF6)2. SCXRD was collected for several single co-crystals of the type

[NixRu1-x(bipy)3](PF6)2 grown from a 0.50:0.50 solution and each had a slightly different set of unit cell parameters (all the same phase). This was not surprising since each had different ratios of Ni:Ru as ascertained by SEM-EDX. Therefore, it was postulated that the collected powder patterns were an overlay of several patterns each with only slight differences in peak positions resulting in broadening due to peak coalescence. The absence of broad peaks for [NixRu1-x(bipy)3][NaCr(ox)3] provides further evidence that composition of the co-crystals is dependent on the composition of the solution and therefore the entire batch of crystals can be represented as [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] instead of

[NixRu1-x(bipy)3][NaCr(ox)3].

5.2.4 [Ru(bipy)3][NaCrxFe1-x(ox)3] (system 2)

The pure compounds [Ru(bipy)3][NaCr(ox)3] and [Ru(bipy)3][NaFe(ox)3] both crystallise as deep red tetrahedra as does the co-crystal compound

[Ru(bipy)3][NaCrxFe1-x(ox)3]. Due to the similarity between the co-crystals and the crystals of the pure compounds, visual inspection was not utilised to assess the success of co-crystallisation. Crystalline material was first observed four days after the initial mixing of the various aqueous solutions listed in Table 20. Co-crystallisation was stopped at two weeks after mixing, at which time the mother liquor was observed to be slightly tinged with red, likely due to a small amount of 2+ free [Ru(bipy)3] in solution. These observations were consistent for all of the replicate experiments attempted.

The vial containing the solutions for the first attempt at synthesising

[Ru(bipy)3][NaCrxFe1-x(ox)3] co-crystals was disturbed during the co-crystallisation period. As a result, many of the crystals that formed were not single. Figure 81 shows an SEM image taken of the crystalline material formed from this first attempt.

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Figure 81: SEM image of crystalline [Ru(bipy)3][NaCrxFe1-x(ox)3] (system 2). The areas outlined in red were analysed at close range due to their acceptable angle with respect to the X-Ray beam. The area outlined in blue highlights an area that was overexposed to the X-ray beam during close range analysis by EDX resulting in slight surface erosion (after a live time of 60 seconds).

None of the EDX results from this batch were treated as single crystal values. However, analysis at both close range and low magnification (bulk analysis) yielded an average Cr:Fe ratio of ca. 0.60:0.40. Experiments for this particular system, 3- 3- starting with a solution containing an equimolar ratio of [Cr(ox)3] and [Fe(ox)3] were repeated an additional time giving a total of four attempts; three of which produced single crystals with well-defined edges and smooth surfaces that closely resembled the [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] co-crystal that is shown in Figure 73 (a) and Figure 77).

This system involves the dilution of the trivalent metal centre in the anionic tris-oxalato complex. The metal dilution component of this experiment can be likened to the K3[CrxFe1-x(ox)3] system (discussed in Section 5.2.1), which was found to yield co-crystals that contained concentration gradients prompted most likely by III 3- solubility differences between the two [M (ox)3] complexes. A representative spectrum taken from a [Ru(bipy)3][NaCrxFe1-x(ox)3] co-crystal is shown in Figure 82. The raw atomic percentages (At%) of the transition metals and their relative ratios are included as insets.

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Formula

[Ru(bipy)3][NaCr0.59Fe0.41(ox)3]

Raw At% Solid Ratio (Cr) 1.22 0.60 (Fe) 0.86 0.40 (Ru) 2.16 1

Figure 82: EDX spectrum from a tetrahedral [Ru(bipy)3][NaCr0.59Fe0.41(ox)3] co-crystal. The blue shaded areas highlight the position of the Na Kα line at 1.1 keV. Quantitative EDX data for the transition metals are given as atomic percentages (At%).

The spectrum shown in Figure 82 shows peaks belonging to chromium, iron (6.4 keV) and ruthenium, which are all attributed to the presence of the respective metal complexes. The low energy area of the spectrum between 0-1.5 keV closely resembles that of the [NixRu1-x(bipy)3][NaCr(ox)3]. Chlorine and potassium peaks are also not observed in the spectra for co-crystals of these systems. EDX spectra of the powder residues resulting from the evaporated mother liquor show large peaks for both potassium and chlorine (see Appendix B).

The quantitative EDX data, which are shown as an inset in Figure 82 gives a Ru:(Cr+Fe) ratio of 1:1 (1.04:1) and a Cr:Fe ratio of 0.60:0.40 (chromium xsolid = 0.59) for this particular co-crystal. Subsequent measurements from the same co-crystal gave very similar results. Multiple EDX measurements of other single co-crystals in this batch (8 co-crystals and 18 measurements) averaged a surface

Ru:(Cr+Fe) ratio of 1:1 ((1.09 ± 0.06):1) and a chromium xsolid value of 0.58 ± 0.01.

The minimum and maximum chromium xsolid values were found to be within two standard deviations of the mean at 0.57 and 0.60 respectively (refer to Table 21). As EDX is a surface technique (reaching depths ca. 5-6 µm), selected single co-crystals that were previously analysed at the surface were crushed and carbon-coated to test for the presence of a concentration gradient. The mean Ru:(Cr+Fe) ratio and chromium xsolid value for crushed single co-crystals were calculated to be 1.00 ±

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0.03:1 and 0.58 ± 0.00. These results are essentially the same as surface measurements.

Repeat experiments yielded similar chromium xsolid values (0.65 ± 0.03, 0.62 ± 0.02, measured on eight and ten single co-crystals respectively), as did a one-off cursory experiment with a starting chromium xsolution value of 0.40 (0.55 ± 0.03, eight single co-crystals). None of the co-crystals were found to contain exclusively chromium or iron nor were any found to contain a high proportion of iron compared to chromium. EDX analysis conducted on the residual solid collected from the evaporated mother liquors showed higher concentrations of iron in relation to chromium. However, since a large proportion of the metal complexes were consumed during co-crystallisation (as indicated by the faint colour of the mother liquor), only a very small amount of solid residue was isolated from each batch. Consequently, the atomic percentages obtained were accompanied by large errors (ca. 50%) (see Appendix B).

Supramolecular selection is a proposed mechanism that attempts to explain the observation where co-crystals from a single batch have different xsolid values. The difference in xsolid values between crystals is thought to come about when one crystal nucleates with a slightly greater proportion of one metal complex while another nucleates with a greater proportion of the other. This variation of the supramolecular selection mechanism results in a single batch of co-crystals that have xsolid values above and below that of the starting xsolution value.

Therefore, supramolecular selection as defined does not explain the observations for this system, since all chromium xsolid values were tightly distributed and were found to be above the initial xsolution value of 0.50. Therefore, unlike co-crystals of the

K3[CrxFe1-x(ox)3] system which do form with concentration gradients, the consistency between surface and crushed measurements provides evidence suggesting that [Ru(bipy)3][NaCrxFe1-x(ox)3] co-crystals do not. This is not surprising since the reaction is conducted in a closed vessel and under constant temperature and a constant volume of water with no additional solvent involved to facilitate crystallisation, such as with vapour diffusion and solvent evaporation methods. The formation and crystallisation of these metal-organic frameworks occur

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3- 3- simultaneously. The geometric dimensions of [Cr(ox)3] and [Fe(ox)3] in these types of structures are very similar with parameters such as MIII-O bond lengths and bite angles only varying by ca. 1.5%.65,290,340 However minute these differences, the 3- findings under these reaction conditions imply that [Cr(ox)3] is slightly more 3- energetically favoured over [Fe(ox)3] during the formation of the

[Ru(bipy)3][NaCrxFe1-x(ox)3] metal-organic framework.

SCXRD data were not collected for this system as the electron densities of Fe3+ and Cr3+ are very similar to one another. Structural information was instead gauged using

PXRD data. The experimental powder pattern for [Ru(bipy)3][NaCrxFe1-x(ox)3] co-crystals is shown in Figure 75 (green trace). The positions, relative intensities of peaks and the FWHM in the experimental pattern are almost identical to the experimental [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] pattern indicating the formation of an isomorphous structure consistent throughout the bulk sample. Although SCXRD data were not collected for this system, a phase change between room temperature and 173 K is unlikely given the similarity of the pattern to the

[Ni0.50Ru0.50(bipy)3][NaCr(ox)3] simulated trace.

II 2+ 5.2.5 Homoleptic cationic and anionic metal dilutions involving [M (phen)3] III 3- and [M (ox)3] (systems 3 and 4)

II 2+ Both the cationic and anionic metal dilution experiments of [M (phen)3] and III 3- [M (ox)3] in the presence of NaCl (1:1:2 ratio) produced red rectangular prismatic 2+ co-crystals. Compounds obtained from the crystallisation of [Ru(phen)3] with 3- 3- 2+ 3- either [Cr(ox)3] or [Fe(ox)3] and [Ni(phen)3] with [Cr(ox)3] in the presence of NaCl produced red and dark pink rectangular prism shaped crystals respectively. It was therefore difficult to use visual inspection as a means to qualitatively screen for co-crystallisation. Co-crystals for both systems began to form one week after the initial mixing of the various solutions listed in Table 20. Co-crystallisation was stopped two weeks after mixing, at which time, the mother liquor was observed to be of the same colour and intensity as the starting solution. On average, only a few co-crystals had formed per batch in comparison to batches of

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II III [M (bipy)3][NaM (ox)3]. All co-crystals appeared to have well-defined edges and lustrous surfaces.

The co-crystals that formed, were found to be unstable and decomposed to a powder shortly after removal from the mother liquor. The characterisation protocol was altered to accommodate this complication. Instead of viewing the crystals under the microscope while placed on slides, the crystals were visually examined while still immersed in the mother liquor. Several attempts were made to collect both single crystal and powder XRD data for these crystals; all attempts resulted in the collection of very poor data. Consequently, XRD was omitted from the protocol for the remaining replicates and hence no structural data are available for these systems. SEM-EDX was the only characterisation technique performed for co-crystals resulting from these systems.

Analysis of single crystals was achieved by transferring the crystals (via pipette, one at a time) directly onto the aluminium stubs, bypassing viewing under the optical microscope. Once adhered to the carbon tape, the crystals were quickly washed with water to remove the residual mother liquor (via pipette) then carbon-coated. SEM-EDX analysis was limited to only a few minutes. Despite the precautions taken, all of the crystals appeared to be physically weathered within moments of analysis. An SEM image of a rectangular prismatic crystal formed by the 2+ 2+ 3- co-crystallisation of a 1:1:2 ratio of [Ni(phen)3] , [Ru(phen)3] and [Cr(ox)3] in the presence of NaCl (system 3) is shown in Figure 83.

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Figure 83: SEM image of a single co-crystal formed by the co-crystallisation of a 1:1:2 ratio of 2+ 2+ 3- [Ni(phen)3] , [Ru(phen)3] and [Cr(ox)3] in the presence of NaCl (system 3). All rectangular prismatic crystals were observed to structurally deteriorate under the SEM vacuum.

Figure 84 showcases representative EDX spectra measured from two single II 2+ III 3- co-crystals resulting from the co-crystallisations of [M (phen)3] and [M (ox)3] in the presence of NaCl (experiment types 3 and 4). Within each spectrum, the solution compositions with respect to the metal complexes are shown in addition to the raw EDX data, which are given as atomic percentages (At%) of the transition metals present in the solid state. Relative ratios involving MII and MIII and associated complexes present in both the solution and solid states are also shown.

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(a) Complex Solution Ratio 2+ [Ni(phen)3] 0.50 2+ [Ru(phen)3] 0.50 3- [Cr(ox)3] 1

Raw At% Solid Ratio (Cr) 0.92 1 (Ni) 0.70 0.75 (Ru) 0.68 0.75

(b) Complex Solution Ratio 2+ [Ru(phen)3] 1 3- [Cr(ox)3] 0.50 3- [Fe(ox)3] 0.50

Raw At% Solid Ratio (Cr) 0.66 0.40 (Fe) 0.83 0.60 (Ru) 2.28 1.50

Figure 84: EDX spectra collected from rectangular prism shaped crystals grown from solutions II 2+ III 3- containing [M (phen)3] and [M (ox)3] in the presence of NaCl. The starting solution for the 2+ 2+ cationic metal dilution experiment (a) contained a 1:1:2 ratio of [Ni(phen)3] , [Ru(phen)3] , and 3- 2+ 3- [Cr(ox)3] . The anionic metal dilution experiment (b) had a 2:1:1 ratio of [Ru(phen)3] , [Cr(ox)3] , 3- and [Fe(ox)3] in the starting solution. The blue shaded areas at 1.1 keV highlight the position of the Na (K) line. Atomic percentages for the transition metals (At%) are given as insets within each spectrum.

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The spectrum shown in Figure 84 (a) is very similar to that shown in Figure 78

([NixRu1-x(bipy)3][NaCr(ox)3]), while the spectrum shown in Figure 84 (b) closely resembles the spectrum shown in Figure 82 ([Ru(bipy)3][NaCrxFe1-x(ox)3]). Each spectrum exhibits peaks that are associated with the metal complexes that were present in solution, namely, Ni (K), Ru (Lβ) and Cr (K) peaks in the upper spectrum

(a) and Ru (Lβ), Cr (K) and Fe (K) peaks for the lower (b). As with previous II III systems of the type [M (bipy)3][NaM (ox)3] that were discussed, both of the spectra in Figure 84 do not have peaks associated with potassium and chlorine. However, unlike these previously discussed systems, peaks associated with sodium at 1.1 keV are absent from these spectra (blue shaded areas). EDX of the solid residue obtained by evaporating the solvent from the mother liquor found sodium, potassium and chlorine in abundance. This is strong evidence to conclude that the crystals formed from these solutions do so without incorporating any sodium or potassium. The absence of a monocation within these crystals forbids a 1:1 stoichiometric II 2+ III 3- relationship between [M (phen)3] and [M (ox)3] in the solid state, given the necessary charge balance required between the two ionic species. This finding indicates that the formation of a framework polymer is improbable.

The quantitative EDX data generated from the spectrum in Figure 84 (a) yields a

(Ni+Ru):Cr ratio of about 1.5:1 and a Ni:Ru ratio close to 1:1 (nickel xsolid = 0.51). Measurements from different areas on the same co-crystal yielded similar values. The ratios obtained and the charges of the metal complexes in solution suggest the formation of co-crystals with the formula [Ni0.50Ru0.50(phen)3]3[Cr(ox)3]2. Similar II III compounds with the general formula [M (phen)3]3[M (ox)3]2·xH2O have been previously reported, synthesised by the simple stoichiometric mixing of aqueous II 2+ III 3- solutions containing [M (phen)3] and [M (ox)3] . Hydration of these materials is described by the authors as “extensive”; where consistent values via elemental microanalysis were only possible when the crystals were allowed to dry. The authors

II III 365 report dried formulae of [M (phen)3]3[M (ox)3]2·15H2O.

A total of eleven co-crystals were measured from this batch (23 measurements), all exhibiting similar EDX spectral profiles and data. The relative ratios between the various transition metals were found to be consistent across all eleven co-crystals. The mean (Ni+Ru):Cr ratio for single crystals in this batch was found to be

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1.55 ± 0.06:1. The mean nickel xsolid value was calculated to be 0.51 with a standard deviation of 0.02. All xsolid values were found to be within two standard deviations of the mean, with minimum and maximum values of 0.47 and 0.55 respectively (refer to Table 21). The statistics for this system are akin to those for the

35,261 [NixRu1-x(phen)3](PF6)2 molecular system (0.50 ± 0.01). Based on these results, the extent of supramolecular selection for this system is almost negligible given the tight distribution of nickel xsolid values centred around 0.50.

Single crystal homogeneity was assessed using EDX measurements from crushed single co-crystals. The EDX measurements from the crushed samples yielded a

(Ni+Ru):Cr ratio of (1.50 ± 0.09):1 and a nickel xsolid value of 0.49 ± 0.02. Both of these values correspond well to those acquired from surface single crystals measurements. This suggests the formation of co-crystals without concentration II 2+ gradients, likely due to the similar solubilities of the two [M (phen)3] in water under these conditions. Again, the nickel xsolid values measured from the residue obtained from the evaporated mother liquor are unreliable due to the direct overlap of chlorine and ruthenium peaks. However, EDX conducted on the residues suggest a final solution composition containing a 1:1 Ni:Ru ratio (0.51 ± 0.02). All of the EDX data collected from this system strongly indicate that the nickel content of the 2+ 2+ co-crystal and by extension [Ni(phen)3] , is dependent on the [Ni(phen)3] (or 2+ [Ru(phen)3] ) concentration in solution. These results are similar to those found for the previously reported [Ni0.50Ru0.50(phen)3](PF6)2 molecular system.

The quantitative EDX data shown as an inset in Figure 84 (b) reveals a Ru:(Cr+Fe) ratio of 1.53:1 and a Cr:Fe ratio close to 0.40:0.60 (chromium xsolid = 0.44). Subsequent measurements from different areas on the same co-crystal yield similar values indicating a homogeneous surface composition. A total of ten co-crystals were measured from this batch, each in two areas giving rise to a total of 20 measurements. All of the EDX results were consistent with the featured spectrum in Figure 84 (b). The mean Ru:(Cr+Fe) ratio for the batch was found to be

(1.67 ± 0.08):1, while the average chromium xsolid value in single crystals was calculated to be 0.44 ± 0.02. All xsolid values were within three standard deviations of the mean with minimum and maximum values of 0.38 and 0.47 respectively. Repeat experiments consistently gave slightly lower chromium xsolid values (0.47 ± 0.01,

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0.48 ± 0.02, ten crystals measured from each). Chromium xsolid values taken from the residue obtained by the evaporation of the mother liquor suggest a final solution containing a higher proportion of chromium (0.62 ± 0.02). This is fitting since the co-crystals that formed were found to be richer in iron.

The EDX measurements taken from the crushed samples yielded a chromium xsolid value of 0.43 ± 0.01. This correlates well to the chromium xsolid value obtained from surface measurements (0.44 ± 0.02). Therefore, unlike co-crystals of the

K3[CrxFe1-x(ox)3] system, which do form with concentration gradients, co-crystals with the suspected formula [Ru(phen)3]3[CrxFe1-x(ox)3]2 have a homogeneous composition. This result further asserts the conclusion made earlier that under these 3- 3- conditions (i.e. constant temperature and water volume), [Cr(ox)3] and [Fe(ox)3] have very similar solubilities.

As with the [Ru(bipy)3][NaCrxFe1-x(ox)3] system, supramolecular selection (as defined within this work) does not explain the observations made here, since all the chromium xsolid values were below the initial xsolution value. The slightly biased 3- distribution of the xsolid values below 0.50, suggests a minor preference for [Fe(ox)3] 3- over [Cr(ox)3] during the formation of these co-crystals. It is worth noting however, 3- that the xsolid values for this system favour [Fe(ox)3] , whereas the xsolid values for the 3- [Ru(bipy)3][NaCrxFe1-x(ox)3] system favour [Cr(ox)3] . The similarity between the two crystallising environments suggests a bias created by a genuine preference for III 3- one [M (ox)3] complex over the other during the formation of these compounds. Again, it seems that a structural difference is being recognised beyond the point of difference even when the variation imparts a very minute change to the overall shape and size of the complex.

The Ru:(Cr+Fe) ratio of 1.49 ± 0.06:1 found for crushed co-crystals compares better than the ratio of 1.67 ± 0.08:1 that was calculated from surface measurements due to the stoichiometry needed to balance the charges between the cationic and anionic complexes. It was mentioned earlier within this section that handling the rectangular prism shaped crystals was problematic, likely due to dehydration. It is likely that these factors largely contributed to the change in the surface topology during analysis, transforming a flat and smooth surface into one that contained many flaws.

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Surface irregularities affect measurements of elements at the lower end of EDX spectra, such as ruthenium (2.6 keV) in the much the same way as the tilt or slant of a sample (see discussion regarding tilt). This known shortcoming of the EDX technique together with the values obtained on crushed samples best explain the overestimated ruthenium content in the surface measurements. Therefore, since the crushed co-crystals are dehydrated and then powdered before being re-coated and re-analysed, the possibility of structural changes during analysis is reduced.

Given the repeated exclusion of sodium from co-crystals resulting from this system, experiments of both systems were repeated twice more (in addition to the triplicates); once with a NaCl concentration of 0.04 M and once without any added NaCl. The EDX results of the co-crystals resulting from the system containing the extra NaCl closely resembled the EDX data of co-crystals formed from the triplicate experiments. The experiment without added NaCl failed to produce any solid II III material. The syntheses reported for the compounds [M (phen)3]3[M (ox)3]2·15H2O, do not include NaCl or any additional salt. The authors describe solutions twice as concentrated as those described for this work but do not stipulate the quality of the crystals that resulted, i.e. large single crystals or a microcrystalline product, nor do they mention the duration of the experiment.365 This suggests that although sodium and chloride are excluded from the co-crystals, one or both of these ions facilitate and/or accelerate co-crystal formation in very dilute solutions.

5.2.6 [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] (system 5) and

[Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3] (system 6)

Unlike experiment types 1-4, which are described as homoleptic co-crystallisations, experiment types 5 and 6 are described as different ligand co-crystallisation II 2+ experiments as they simultaneously attempted to co-crystallise [M (bipy)3] with II 2+ II 3- [M (phen)3] (M = Ni, Ru) in the presence of [Cr(ox)3] and NaCl. Different II 2+ II 2+ - ligand experiments involving [M (bipy)3] and [M (phen)3] with PF6 as the counterion have been attempted in previous projects but failed to produce single co-crystals of homogeneous compositions. Instead, red/orange co-crystals were observed where block-shaped crystals appeared to be penetrated by a rod-shaped

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CHAPTER 5 crystal, such that the resulting complicated crystalline morphology resembled that of a necklace.154 Secondary and backscattered SEM images of crystals obtained from a previous experiment that were grown from a solution containing a 0.50:0.50 mixture of [Ni(phen)3](PF6)2 and [Ru(bipy)3](PF6)2 are shown in Figure 85. SEM-EDX analyses of blocks indicated a [Ni(phen)3](PF6)2 concentration of ca. 90% (i.e. 10%

[Ru(bipy)3](PF6)2), while the needles were found to contain ca. 90%

[Ru(bipy)3](PF6)2. Approximately equimolar ratios of both complexes were found at the interface between the two crystal morphologies.261,306

(a) (c)

(b) (d)

Figure 85: SEM images of “necklace” co-crystals that were grown from a solution containing an equimolar mixture of [Ru(bipy)3](PF6)2 and [Ni(phen)3](PF6)2 detected using secondary electrons (a and b) and backscattered electrons (c and d). The upper images show a single well-defined block shaped crystal penetrated by a needle; the lower images show a much more complicated morphology. The backscattered images clearly show the contrast between ruthenium-rich/nickel-poor (bright) and ruthenium poor/nickel rich (dark) areas.261,306

The EDX spectra of two single co-crystals, grown from solutions containing II 2+ II 2+ II equimolar concentration of both [M (bipy)3] and [M (phen)3] (M = Ni or Ru) are shown in Figure 86. The top spectrum (a) was obtained from a crystal grown 2+ 2+ from a solution containing [Ni(bipy)3] and [Ru(phen)3] (experiment type 5); the crystal from which the lower spectrum (b) was measured was grown from a solution

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2+ 2+ containing [Ni(phen)3] and [Ru(bipy)3] (experiment type 6). Both types of 3- crystals were grown in the presence of [Cr(ox)3] and NaCl resulting in a solution Ni:Ru:Cr:Na ratio of 0.50:0.50:1:2. All crystals resulting from these experiments were red, of similar size and exhibited a tetrahedral crystal habit. The formula and raw atomic percentages (At%) of the transition metals and their relative ratios are included as insets in each spectrum.

(a) Formula

[Ni(bipy)3]0.80[Ru(phen)3]0.20 [NaCr(ox)3]

Raw At% Solid Ratio (Cr) 1.77 1 (Ni) 1.38 0.80 (Ru) 0.39 0.20

(b) Formula

[Ni(phen)3]0.20[Ru(bipy)3]0.80 [NaCr(ox)3]

Raw At% Solid Ratio (Cr) 1.83 1 (Ni) 0.36 0.20 (Ru) 1.46 0.80

Figure 86: EDX spectra measured from crystals grown from co-crystallisation types 5 (a) and 6 (b) with the formula [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] and [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] respectively. Note that in both spectra the peak intensity of II 2+ the metal associated with the [M (phen)3] complex much less than for the peak associated with the II 2+ metal of the [M (bipy)3] complex. Quantitative EDX data for the transition metals are given as atomic percentages (Raw At%).

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The two spectra shown in Figure 86 are very similar to one another in a qualitative sense. They both contain peaks belonging to chromium, nickel and ruthenium, 3- II 2+ indicating that each of the co-crystals contained [Cr(ox)3] , [M (bipy)3] and II 2+ [M (phen)3] . Furthermore, both spectra show evidence of sodium but neither contains peaks attributed to chlorine or potassium. EDX spectra of the powder residues resulting from the evaporated mother liquors show large peaks for both potassium and chlorine (see appendix B).

The atomic percentages generated from both the upper and lower spectra shown in

Figure 86 give (Ni+Ru):Cr ratios close to 1:1. The nickel xsolid values of 0.78 (a) and II 2+ 0.20 (b) suggest a strong bias towards the [M (bipy)3] complex during co-crystallisation. Subsequent measurements from different areas on these co-crystals confirm these values, as do the measurements made from other co-crystals within the respective batches. Mean (Ni+Ru):Cr ratios were found to be 1.06 ± 0.03:1 and 1.04 ± 0.04:1 for systems 5 and 6 respectively.

Multiple EDX measurements taken from nine [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] single co-crystals (18 measurements) averaged a surface nickel xsolid value of

0.77 ± 0.02. The minimum and maximum nickel xsolid values were found to be within two standard deviations of the mean at 0.74 and 0.80 respectively. EDX analysis conducted on twelve [Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3] single co-crystals (25 measurements) revealed a mean nickel xsolid value of 0.20 ± 0.03. All nickel xsolid values for this system were within one standard deviation of the mean with minimum and maximum values calculated to be 0.18 and 0.23 respectively. Statistical data for both systems are summarised in Table 21.

The nickel xsolid values calculated for co-crystals of both systems suggest that under II 2+ these conditions, the inclusion of [M (bipy)3] complexes are favoured over II 2+ [M (phen)3] in the solid state by a ratio of 4:1. All three triplicate co-crystallisations (nickel xsolution of 0.50) for both of these systems yielded the same II 2+ II 2+ 4:1 ratio between [M (bipy)3] and [M (phen)3] . No co-crystals were found to exclusively contain nickel or ruthenium. Supramolecular selection as defined earlier does not explain these observations, since all nickel xsolution values were tightly distributed around 0.80 for [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] (system 5) and

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0.20 [Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3] (system 6) and not centred around the initial xsolution value of 0.50. EDX analysis conducted on the residual solid collected from the evaporated mother liquors showed a high concentration of the metal II 2+ associated with the [M (phen)3] complex relative to metal associated with II 2+ [M (bipy)3] .

In retrospect, the design of these different ligand experiments had the intrinsic potential to produce crystals that contained concentration gradients. This is because II 2+ homoleptic co-crystallisation experiments involving [M (phen)3] (experiment types II 2+ 3 and 4) took twice as long to form crystals than their [M (bipy)3] analogues

(experiment types 1 and 2). However, the mean (Ni+Ru):Cr ratios and nickel xsolid values for crushed single co-crystals were calculated to concur with surface measurements; (Ni+Ru):Cr ratios and nickel xsolid values of 1.02 ± 0.01:1 and 0.78 ± 0.01 (for experiment type 5) and 0.99 ± 0.04:1 and 0.22 ± 0.02 (for experiment type 6). The results obtained from surface and crushed measurements do not imply the formation of co-crystals with concentration gradients, instead they support the notion II 2+ of a ca. 20% threshold for [M (phen)3] throughout a homogeneously composed co-crystal.

II 2+ In an attempt to incorporate more [M (phen)3] into the resulting co-crystals, both types of experiments were repeated twice more with a starting xsolution value of 0.80 in II 2+ favour of the [M (phen)3] complex. Interestingly, only a few crystals were observed to form from these experiments after a duration of 13 days, all of which were found to contain nickel and ruthenium. All the crystals were red, tetrahedral and stable under atmospheric and vacuum conditions. Despite the substantial surplus II 2+ II 2+ II 2+ of [M (phen)3] present in solution, the solid state [M (bipy)3] :[M (phen)3] ratio was found to consistently be 4:1, suggesting the constant formation of a structure II 2+ with a 20% threshold for [M (phen)3] complexes.

X-ray diffraction data were collected for both [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3]

(system 5) and [Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3] (system 6) co-crystals in order to better understand the SEM-EDX results. Single crystal refinement data for both types of co-crystals are provided in Table 22. Powder XRD patterns are shown in

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Figure 75 and are indexed against the [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] simulated pattern.

The topology exhibited for both types of co-crystal shows the same chiral 3D arrangement as that discussed for [Ni0.50Ru0.50(bipy)3][NaCr(ox)3], where the formal 2- [NaCr(ox)3] units represent three connecting nodes to form a 3-connected 10-gon (10, 3) framework. Both structures are isomorphous with

[Ni0.50Ru0.50(bipy)3][NaCr(ox)3] and hence with the cubic structures listed in Table

19. The unit cell parameters for [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] (a = 15.4664(4) Å, V = 3699.68(15) Å3) are smaller than those found for

[Ni0.50Ru0.50(bipy)3][NaCr(ox)3]. The parameters found for

[Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3] are smaller still, with a = 15.4642(3) Å and V = 3698.17(12) Å3. It is very interesting that despite containing the bulkier II 2+ [M (phen)3] complex, the unit cells for both of these co-crystals are significantly II 2+ smaller than any [M (phen)3] containing structure listed in Table 19 . Looking further into the structures summarised in Table 19, is noted that every framework 2- II 2+ containing the [NaCr(ox)3] unit together with [M (bipy)3] has a structure with a larger unit cell than those found for [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] and II 2+ [Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3]. Also, of all of the [M (bipy)3] containing structures listed in the same table (MII = Ni, Ru), only those containing formal I III 2- 2- [M M (ox)3] units that are known to form smaller cells such as [LiCr(ox)3] and

2- 310,340,367 [NaAl(ox)3] do so. These results indicate that co-crystallisation of II 2+ II 2+ II [M (phen)3] with [M (bipy)3] (M = Ni, Ru) to form

[Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] or [Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3] leads II 2+ to slightly more efficient crystal packing than when [M (bipy)3] is incorporated alone.

As with the structure for [Ni0.50Ru0.50(bipy)3][NaCr(ox)3], there is one-third of a 2- + 3+ formal [NaCr(ox)3] unit i.e. one oxalato ligand bridging a Na and Cr ion, in the asymmetric unit in the structures of [Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] and

[Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3]. However, for both of these structures there is II 2+ II 2+ a third of a [M (bipy)3] molecule and a third of a [M (phen)3] molecule (albeit in partial occupancy) in the asymmetric unit. The position of the MII site in the II 2+ II [M (bipy)3] molecule shares the same coordinates with the M site for the

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II 2+ [M (phen)3] . The position of the Ni/Ru site in

[Ni(bipy)3]x[Ru(phen)3]1-x[NaCr(ox)3] was modelled as a disordered mixture of Ni and Ru; the relative occupancies were refined (with fixed and equivalent displacement parameters) to be 0.79 Ni and 0.21 Ru. The refined occupancy of the

Ni/Ru site for [Ni(phen)3]x[Ru(bipy)3]1-x[NaCr(ox)3] was modelled using the same method and was found to be 0.19 Ni and 0.81 Ru. These values agree very closely with those obtained by the SEM-EDX results, which showed a 4:1 solid state ratio of II 2+ II 2+ [M (bipy)3] to [M (phen)3] in co-crystals that crystallise from solutions containing an equimolar ratio of the two complexes. Therefore, the final refinement cycles were conducted with the relative occupancies fixed at 0.80 in favour of the II 2+ metal associated with the [M (bipy)3] complex.

It has been well established since the inception of these framework materials that the II 2+ chirality of the [M (L)3] complex (L = 2,2′-bipyridine, 1,10-phenanthroline) serves I III 2- as a chiral template for the formation of the 3D helical {[M M (ox)3] }n anionic II 2+ framework. When a Δ-[M (L)3] complex is used, the metal centres about each I III 2- [M M (ox)3] complex unit also exhibit a Δ configuration (and vice versa). When a racemic mixture is used (such as within this research), spontaneous resolution is observed whereby each single crystal is homochiral however the bulk sample contains single crystals of both Δ and Λ chirality. This was the result obtained for the

[Ni0.50Ru0.50(bipy)3][NaCr(ox)3] co-crystallisation system.

It is therefore extremely surprising that co-crystallisation experiments involving II 2+ II 2+ 2- [M (bipy)3] and [M (phen)3] with [NaCr(ox)3] resulted in heterochiral single co-crystals of the formula [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] and II 2+ [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3]. In these systems the [M (bipy)3] II 2+ complex is observed to exhibit the opposite chirality to the [M (phen)3] units, such that none of the carbon atoms associated with 2,2′-bipyridine shares coordinates with those belonging to 1,10-phenanthroline. The coordinates of the nitrogen atoms are observed to remain constant regardless of the metal complex occupying the cavity. However, nitrogen atoms associated with each of the observed 1,10-phenanthroline ligands belong to two 2,2′-bipyridine ligands (and vice versa). Therefore, the relative II 2+ II 2+ occupancies of the nitrogen atoms associated with [M (bipy)3] and [M (phen)3] were fixed at 0.80 and 0.20 respectively. The configurations of the metal centres of

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CHAPTER 5 the helical anionic framework share the same chirality as that exhibited by II 2+ II 2+ [M (bipy)3] suggesting that for these systems only [M (bipy)3] complexes act as a template for the formation of the anionic framework.

2+ Figure 87 shows the non-superimposable relationship between the Λ-[Ru(bipy)3] 2+ and Δ-[Ni(phen)3] complexes of the formula

[Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] along the [100] axis and from a perspective view that shows all of the ligands coordinated to the Ni/Ru site. The 2+ [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] structure contains Λ-[Ni(bipy)3] and 2+ Δ-[Ru(phen)3] units and closely resembles that of

[Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3]. Although both of the structures discussed II 2+ II 2+ here contain Λ-[M (bipy)3] and Δ-[M (phen)3] units, single crystals containing II 2+ II 2+ Δ-[M (bipy)3] and Λ-[M (phen)3] were found from each co-crystallisation batch. Due to the similarities between the structures, the following discussion focuses on the [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] structure; the findings (i.e. bond lengths, angles etc.) for the [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] structure are summarised in Appendix F.

2+ 2+ Figure 87: The Λ-[Ru(bipy)3] and Δ-[Ni(phen)3] complexes in [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] as viewed along the [100] plane (left) and a perspective that shows all of the ligands associated with the Ni/Ru site (right). The carbon atoms associated with 2,2′-bipyridine are shown in black while those belonging to 1,10-phenanthroline in red. Nitrogen atoms are shown in blue, the magenta represents the Ni/Ru site. Hydrogen atoms are not shown.

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2+ 2+ Figure 88 shows the positions of Λ-[Ru(bipy)3] and Δ-[Ni(phen)3] complexes (three of each) as viewed along the [100] axis and from a perspective that shows the overlap of the 1,10-phenanthroline carbon atoms belonging to neighbouring complexes.

2+ 2+ Figure 88: Three adjacent Λ-[Ru(bipy)3] and Δ-[Ni(phen)3] complexes in [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] as viewed along the [100] axis (left) and a perspective that 2+ shows the overlap of the 1,10-phenanthroline carbon atoms (right). The Λ-[Ru(bipy)3] complexes 2+ are shown in black while carbon atoms associated with the Δ-[Ni(phen)3] complexes are shown in red. The distance between Ni/Ru sites of neighbouring complexes is 9.470 Å.

For the [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] structure, each carbon atom associated with an observed 1,10-phenanthroline ligand is assigned to Ni while each and 2,2′-bipyridine ligand is assigned to Ru. This is possible due to the inert character of Ru2+ polypyridyl complexes with respect to ligand exchange.59,60 The 2+ crystal refinement was unstable when the partial occupancy of Δ-[Ni(phen)3] complexes exceeded 0.20. Looking at Figure 88, it appears that at full occupancy of 2+ Δ-[Ni(phen)3] , each 1,10-phenanthroline ligand from a single complex would clash with two other ligands, one each from two neighbouring complexes; hence each complex would overlap with six others. This observation suggests that the partial occupancy of the 1,10-phenanthroline carbons in the orientation shown in Figure 88 2+ 2+ cannot exceed 0.14 i.e. six [Ru(bipy)3] complexes to one [Ni(phen)3] complex in the orientation shown. However, both the SEM-EDX results and the occupancy II 2+ refinement of the M site indicated a [Ni(phen)3] concentration of ca. 20%. Given this evidence and since the cavity in which these complex cations occupy is largely spherical, another orientation or orientations of 1,10-phenanthroline carbons with

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CHAPTER 5 partial occupancies totalling 0.06 must also be present. These carbon atoms were not observed and hence not modelled in the crystal refinement. Assuming that only one additional orientation of 1,10-phenanthroline carbons is present, a carbon atom at 6% occupancy would equate to an electron density of about a third of a hydrogen atom. Therefore, the final refinement cycles were conducted with the relative occupancies of the 1,10-phenthroline carbons (in the orientation shown in Figure 88) fixed at 0.14.

The distance between Ni/Ru sites of neighbouring complexes is 9.470 Å (9.471 Å for

[Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3]), which is shorter than the distance found between Ni/Ru sites in [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] (9.492 Å) despite the larger size of the 1,10-phenanthroline ligand compared to 2,2′-bipyridine.

Just as for the [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] structure, each oxalato ligand bridges adjacent Na+ and Cr3+ ions in all three dimensions giving rise to the well established II 2+ II 2+ anionic helical framework. The [M (bipy)3] /[M (phen)3] are located within the 2- voids produced by the polymeric [NaCr(ox)3] framework. These structures do not contain a void volume; hence, it is not surprising that water was not found within these structures.

The mean MII-N bond length of 2.063(3) Å found for the

[Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] structure is closer to the average Ru-N 2+ bond length present in [Ru(bipy)3] complexes (2.057 Å). This is fitting since a 2+ II large proportion of the cationic guests are [Ru(bipy)3] . The average M -N bond length present in the [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] structure is longer at 2.077(4) Å, a value closer to the literature values for Ni-N bond lengths for 2+ [Ni(bipy)3] guests (2.088 Å). The 2,2′-bipyridine bite angles of 81.28(15)° and

80.45(15)° for [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] and

[Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] respectively are larger than those 2+ 2+ previously observed for [Ni(bipy)3] or [Ru(bipy)3] (78.39-79.39°). The deviation II 2+ from the norm in the bite angle is more greatly pronounced for the [M (phen)3] complex in both of these structures with values refining close to 90°. The 2+ [Ru(bipy)3] guest complex in [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] may be described by a twist angle of 54.12° and an s/h ratio of 1.41. Although the twist angle

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2+ for the [Ni(phen)3] guest complex is much larger at 65.88°, a value quite unusual for these complexes, the centroids and nitrogen atoms used to calculate the s and h values remain the same and hence the s/h ratio is the identical for both. The twist 2+ 2+ angle for the [Ni(bipy)3] and [Ru(phen)3] guest complexes in the

[Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] are measured to be similar to those of

[Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] at 52.81° and 67.19° respectively. The s/h for this structure is also calculated to be 1.41. These values correspond to a trigonally II 2+ twisted and compressed octahedron. The inclusion of the bulkier [M (phen)3] complex seems to have caused some structural strain in these compounds but not enough to form crystals of a different phase to [Ni0.50Ru0.50(bipy)3][NaCr(ox)3].

The Cr-O and Na-O bond lengths do not vary significantly from those discussed regarding [Ni0.50Ru0.50(bipy)3][NaCr(ox)3], nor do the bite and twist angles and s/h ratios. The similarities in the various parameters of the anionic net between II 2+ [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] and the [M (phen)3] containing structures indicates that the framework is unperturbed by the inclusion of the bulker cationic complex. All of the measurements and crystal parameters regarding all three structures discussed within this chapter are summarised in Table 22 and Appendix F.

II 2+ The experimental powder patterns for these [M (phen)3] containing co-crystals are shown in Figure 75 (purple and blue traces). The positions of peaks in the experimental patterns agree well with the profiles of the

[Ni0.50Ru0.50(bipy)3][NaCr(ox)3] simulated trace. This indicates that the single crystal data are representative of the bulk phase and that only one phase is present in the bulk sample. The relative intensity of the [210] and [211] peaks from the same peaks in the other patterns is the only notable difference between the patterns in Figure 75. The FWHM of the peaks in the experimental pattern are also comparable to those of the other patterns in Figure 75. Again, the similarity of the powder patterns to the simulated pattern indicates that the phase and unit cell dimensions remain relatively constant between room temperature and 173 K.

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5.3 Chapter summary and conclusions

Several novel framework co-crystals and crystals exhibiting epitaxial growth were III 3- III prepared using [M (ox)3] metal complexes as molecular building-blocks (M = Cr,

Fe; ox = oxalate). Co-crystals with the formula K3[CrxFe1-x(ox)3]·2.5H2O were analysed using single crystal surface and confocal Raman spectroscopic mapping, SEM-EDX and PXRD and were found to exhibit directional intracrystal concentration gradients. Different epitaxial growth patterns were observed depending on the method used to immerse the seed crystals into the solution. Epitaxial experiments also indicated that supramolecular interactions between like and different complexes are similar enough to allow simultaneously growth to occur on both types of crystals but that interactions between like complexes are slightly more favourable.

II III Four different [M (L)3][NaM (ox)3] co-crystals were prepared by co-crystallising II II [M (L)3]Cl2 (M = Ni, Ru; L = 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen)) III III with K3[M (ox)3] (M = Cr, Fe) in the presence of NaCl. Co-crystals were characterised using SEM-EDX, SCXRD and PXRD. All four of these coordination frameworks were found to be isomorphous. [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] co-crystals were found to have the same ratio of the metal complexes that was II 2+ present in solution indicating that [M (bipy)3] complexes engaged in negligible supramolecular selection. Results for [Ru(bipy)3][NaCr0.60Fe0.40(ox)3] co-crystals suggested that K3[Cr(ox)3] was slightly favoured over K3[Fe(ox)3].

II 2+ II 2+ A [M (bipy)3] : [M (phen)3] ratio of 4:1 was found for co-crystals of both A B A B [M (bipy)3]0.80[M (phen)3]0.20[NaCr(ox)3] (M , M = Ni, Ru) despite some II 2+ experiments containing a four-fold excess of the [M (phen)3] complex. These II 2+ results indicated a ca. 20% threshold for [M (phen)3] is allowed in the framework II 2+ structure of these materials. It was also discovered that the [M (phen)3] molecules II 2+ in both structures exhibited the opposite chirality to the [M (bipy)3] complexes such that single co-crystals had the general formula A B Λ-[M (bipy)3]0.80Δ-[M (phen)3]0.20Λ-[NaCr(ox)3].

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CHAPTER 6: Project Summary and conclusions

6.1 Overall project summary and conclusions

Several novel co-crystalline materials, which have the potential to exhibit tunable properties and/or multifunctionality, were engineered through the exploitation of known supramolecular motifs and architectures. The synthesis of these new materials was achieved by incorporating known amounts of different metal complexes into single crystals to form single co-crystals.

For each system examined, the aim was to gain a deeper understanding of crystal engineering and factors influencing molecular recognition and in turn supramolecular selection. Specific focus was placed on the influence of several factors, which were postulated could affect the ability for metal complexes to engage in molecular recognition for like complexes, such as ligand type and size, metal complex charge, mode of intermolecular interaction and the dimensionality of the eventuating structures. The influences of these factors on supramolecular selection were investigated through the preparation of various binary homoleptic and different ligand experiments. Through the study of these experiments, a greater understanding of the limits of co-crystallisation has been achieved.

Of particular interest were the syntheses of co-crystalline materials that are known to form molecular structures such as those that propagate using the 2D terpy embrace. Those that are known to form 3D framework structures through the polymerisation III 3- of [M (ox)3] building-blocks were also of specific focus. Each type of experiment provided the potential to yield single co-crystals that were capable of exhibiting tunable properties and/or multifunctionality due to the nature of the metal complexes involved. The following subsections summarise the results and provide conclusions specific for each type of co-crystallisation system that was examined.

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6.2 Novel molecular co-crystals formed through the use of the 2D terpy motif

A series of co-crystallisation experiments was conducted involving complexes that exhibit the 2D terpy embrace. Experiments ranged from homoleptic experiments and different ligand experiments involving only complexes with S4 molecular symmetry to different ligand experiments involving the co-crystallisation of complexes with S4 symmetry with those of D3 symmetry. Co-crystals were characterised using SEM-EDX, SCXRD and PXRD techniques.

II II Co-crystals of the general formula [M xRu1-x(terpy)2](PF6)2 (M = Fe, Co, Ni, Cu) were found to form without concentration gradients, as SEM-EDX analysis showed that measurements made from the same co-crystal (surface and crushed measurements) were similar. However, the SEM-EDX results showed that co-crystals grown from the same solution were found to have a range of concentrations such that xsolid single crystal 1 ≠ xsolid single crystal 2. This result is indicative of supramolecular selection between complexes where intermolecular interactions between like complex pairs are slightly more energetically favoured than interactions between different complexes. Variations between xsolid values found for co-crystals II II harvested from the same batch for [M xRu1-x(terpy)2](PF6)2 (M = Co, Ni or Cu) were comparable to one another and significantly larger than for

[FexRu1-x(terpy)2](PF6)2. This strongly suggests that [Fe(terpy)2](PF6)2 and

[Ru(terpy)2](PF6)2 metal complexes engage in the least amount of supramolecular selection during co-crystallisation compared to the other systems.

The results obtained from these experiments with regard to supramolecular selection II 2+ are very interesting, as regardless of the metal centre, various [M (terpy)2] complexes have very similar dimensions. Furthermore, the intermolecular interactions involved in the 2D terpy embrace occur between the ligands of neighbouring coordination spheres of complex pairs. Hence, the results obtained here suggest that even a relatively small change (difference in metal centres) is being recognised beyond the point of difference resulting in molecular recognition and therefore supramolecular selection during co-crystallisation. This is despite the point of difference being completely shrouded by the ligands.

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Powder XRD data revealed different crystal structures were possible for the various II [M xRu1-x(terpy)2](PF6)2 co-crystals despite the similarities between the systems i.e. II II the isomorphous relationship of [M (terpy)2](PF6)2 complexes (M = Co, Ni, Cu).

Co-crystals of the formula [FexRu1-x(terpy)2](PF6)2 were found to adopt the

[Fe(terpy)2](PF6)2 phase without any evidence of phase impurities. Co-crystals of

[CuxRu1-x(terpy)2](PF6)2 were found to predominantly adopt the [Cu(terpy)2](PF6)2 phase with the possibility of only minor phase impurities. The powder XRD patterns for [CoxRu1-x(terpy)2](PF6)2 and [NixRu1-x(terpy)2](PF6)2 were very similar II suggesting the two are isomorphous but did not match either [M (terpy)2](PF6)2 II (M = Co, Ni) nor [Ru(terpy)2](PF6)2. This suggests that [CoxRu1-x(terpy)2](PF6)2 and

[NixRu1-x(terpy)2](PF6)2 co-crystals formed a new structure as a result of co-crystallisation. PXRD patterns suggested that the [Ru(terpy)2](PF6)2 phase was II absent from every [M xRu1-x(terpy)2](PF6)2 batch. This is not surprising as each co-crystal was found to contain both metal complexes and introducing even the slightest change into the high symmetry [Ru(terpy)2](PF6)2 lattice would force the cell into a lower symmetry crystal structure.

II Co-crystals of the general formula [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 were found to have slight concentration gradients, as measurements from crushed samples II showed slightly higher ratios of [M (terpyOH)2](BF4)2 than was found on the surface. Analysis of the residue obtained from evaporating the mother liquors found high proportions of ruthenium, indicating that [Ru(terpy)2](BF4)2 is more soluble in II the co-crystallisation solutions than [M (terpyOH)2](BF4)2. SEM-EDX analysis of II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 systems found that single co-crystals grown from the same solution ranged in composition i.e. xsolid single crystal 1 ≠ xsolid single crystal 2. II Like the [M xRu1-x(terpy)2](PF6)2 systems, this is indicative of supramolecular selection for like complexes during co-crystal growth. Systems where MII = Fe, Cu displayed less supramolecular selection than when MII = Ni. This suggest that 2+ 2+ [Ru(terpy)2] has more favourable intermolecular interactions with [Fe(terpyOH)2] 2+ 2+ and [Cu(terpyOH)2] than with [Ni(terpyOH)2] .

Despite the larger differences between the complexes, the variations between xsolid II values from [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals harvested from the same solution were comparable or smaller than the variations found for

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II [M xRu1-x(terpy)2](PF6)2 systems. This is likely due to the solubility of II [Ru(terpy)2](BF4)2 complexes relative to [M (terpyOH)2](BF4)2 as a larger proportion of [Ru(terpy)2](BF4)2 was left behind in solution. Hence, more II 2+ [M (terpyOH)2] complexes were present in the co-crystals at every stage of II 2+ co-crystallisation leading to the selection bias towards [M (terpyOH)2] during co-crystal growth.

Single crystal and powder XRD analysis of each II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 batch found the co-crystals to be isomorphous II with the respective pure [M (terpyOH)2](BF4)2 compound that was present in solution. The XRD patterns showed no evidence of the [Ru(terpy)2](BF4)2 phase in any of the batches formed from 0.50:0.50 solutions. This strongly suggests that the II 2D terpy supramolecular motif for [M (terpyOH)2](BF4)2 was the dominate motif and therefore more robust than that of [Ru(terpy)2](BF4)2 as it was the structure favoured in co-crystals resulting from each experiment.

II Experiments where [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 co-crystals were formed II II from solutions containing 5% [M (terpyOH)2](BF4)2 (M = Fe, Cu) were found to adopt exclusively the tetragonal I41/a [Ru(terpy)2](BF4)2 phase. Analogous experiments containing 5% [Ni(terpyOH)2](BF4)2 formed monoclinic co-crystals II 2+ II (P21). This signifies that a larger proportion of [M (terpyOH)2] complexes (M =

Fe, Cu) can be accommodated into the [Ru(terpy)2](BF4)2 structure than can 2+ [Ni(terpyOH)2] . The powder XRD patterns suggest that the [Ru(terpy)2](BF4)2 2D terpy supramolecular motif was the dominant motif when the concentration of II 2+ II [M (terpyOH)2] (M = Fe, Cu) complexes were ca. 5%. The powder XRD results from experiments where [Ni(terpyOH)2](BF4)2 was co-crystallised with

[Ru(terpy)2](BF4)2 in 0.50:0.50 and 0.05:0.95 ratios suggested that the resulting co-crystals were isomorphous with crystals of pure [Ni(terpyOH)2](BF4)2. This indicates that perhaps the [Ni(terpyOH)2](BF4)2 structure is more robust compared to II the other [M (terpyOH)2](BF4)2 as it was maintained even when ca. 95% of the complexes in the co-crystals were [Ru(terpy)2](BF4)2.

It is interesting that the combinations that produced co-crystals of the I41/a

[Ru(terpy)2](BF4)2 phase were the same as the 0.50:0.50

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II [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 experiments that displayed the least supramolecular selection. This is further evidence to suggest that [Ru(terpy)2](BF4)2 II complexes are structurally more similar to [M (terpyOH)2](BF4)2 complexes when MII = Fe, Cu than when MII = Ni.

Experiments where [Co(terpyO)(terpyOH)](BF4)2 was co-crystallised with

[Ru(terpy)2](BF4)2 resulted in samples that contained only pure crystals of both complexes. Crystals of pure complexes were also obtained from experiments where II II [M (terpyPh)2](PF6)2 (M = Fe, Ni, Cu) were co-crystallised with [Ru(terpy)2](PF6)2 and experiments where [Ni(L)3](PF6)2 (L = phen, bipy) were co-crystallised with

[Ru(terpy)2](PF6)2 or [Ru(terpyPh)2](PF6)2. Regardless of the differences between each of the complexes involved, the molecular structures of complexes in the each pair were theoretically capable of engaging in some combination of intermolecular interactions to yield co-crystals containing both complexes. However, the results suggest that exclusive supramolecular selection occurred, as only pure crystals eventuated from these experiments, most likely because the supramolecular interactions of the two complexes in each experiment were too different. These combinations are therefore beyond the limit for which molecular recognition processes can be confused into co-crystallising different molecules. It is important to note that exclusive supramolecular selection is the usual result of recrystallisation and is why recrystallisation is considered such a good technique for purification. Ultimately, it seems that the supramolecular motifs of the complexes in each combination were not robust enough to allow both types of complex to exist in the same lattice.

III 6.3 Co-crystallisations using the K3[M (ox)3] metal complex building-block to form novel co-crystalline metal-organic frameworks.

III A variety of co-crystallisation and epitaxial experiments involving the K3[M (ox)3] metal complex building-block were conducted. Single crystals of five novel co-crystalline coordination frameworks were prepared and characterised using single crystal and bulk measurement techniques. Another five novel crystals exhibiting epitaxial growth were prepared and characterised.

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Several homoleptic experiments, which involved the co-crystallisation of two III III different K3[M (ox)3]·xH2O complexes (M = Mn, Cr, Fe, Ru and Rh and xsolution = 0.10 to 0.90 in fractional increments of 0.20) to form co-crystals of the A B general formula K3[M xM 1-x(ox)3]·xH2O were conducted.

Only experiments where solutions of K3[Cr(ox)3] were mixed with solutions of

K3[Fe(ox)3] produced single co-crystals. All other combinations produced either polycrystalline, amorphous or decomposed materials. Experiments involving the stable K3[Cr(ox)3] that produced decomposed products indicated that K3[Cr(ox)3] did not have a stabilising effect during co-crystallisation. Powder XRD measurements of

K3[CrxFe1-x(ox)3]·2.5H2O co-crystals resulting from all batches indicated that the co-crystal phase was isomorphous with pure K3[Cr(ox)3]·2.5H2O and

K3[Fe(ox)3]·2.5H2O and without phase impurities. This was not surprising as

K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O are isomorphous, belonging to the P21/c space group.

The solid state compositions (xsolid) of K3[CrxFe1-x(ox)3]·2.5H2O single co-crystals from all batches were initially examined using SEM-EDX spot analysis. The relative ratios from the same co-crystal were found to differ, with the largest variations observed for co-crystals formed from equimolar solutions (xsolution = 0.50). Further analysis of co-crystals grown from an additional batch where xsolution = 0.50 implied the presence of a directional surface concentration gradient, where the fraction of

K3[Cr(ox)3]·2.5H2O was always found to be greater near the edges (ca. 90%) than at the centre of the co-crystal face (ca. 40%). Line maps conducted along transects spanning diagonally across the largest facet confirmed the formation of a directional concentration gradient. SEM-EDX analysis was limited to ca. 30 minutes per co-crystal, at which time the co-crystals were observed to have deteriorated completely.

Molar fractions of K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O in single co-crystals were instead estimated using the position of the Raman carbonyl stretching peak. This characterisation method was first calibrated using the positions of the peaks for the pure samples, and then validated using SEM-EDX measurements obtained from similar locations on the same co-crystals. Fractions estimated from the Raman

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CHAPTER 6 spectra were found to correlate well with SEM-EDX results. Therefore, single crystal Raman spectroscopic mapping was found to be a suitable alternative analytical technique to SEM-EDX for the quantitative characterisation of these samples.

All co-crystals were observed to contain a directional concentration gradient on the surface of the largest facet. It was found that K3[Cr(ox)3]·2.5H2O concentrations gradually increased from ca. 35-40% at the face centre to ca. 85-90% at the edge.

Estimates of the K3[Cr(ox)3]·2.5H2O concentration at various depths below the surface were obtained using confocal Raman microscopy. Depth-profiles from measurements taken along transects parallel to the largest facet showed a steady decrease of the K3[Cr(ox)3]·2.5H2O concentration towards the centre of the co-crystal. These results followed the same trend as that obtained from surface maps; however, they were not as pronounced. The variations in the K3[Cr(ox)3]·2.5H2O concentrations were found to be very minimal along transects that were perpendicular to the largest facet. None of the co-crystals analysed where found to have areas on or below the surface with K3[Cr(ox)3]·2.5H2O concentrations of less than 30%. The large concentration gradients found on the surface of

K3[CrxFe1-x(ox)3]·2.5H2O co-crystals and the difference between the results obtained by the parallel and perpendicular confocal experiments suggested favourable propagation of crystal growth in some directions but not others during co-crystallisation. The presence of a concentration gradient presents the potential for a single crystal to display an infinitely varying degree of multifunctionality.

Epitaxial crystal growth experiments where seed crystals of the general formula III III K3[M (ox)3]·2.5H2O (M = Cr and/or Fe) were immersed into saturated solutions of III III K3[M (ox)3](aq/EtOH) (M = Cr, Fe or a 1:1 mixture) were conducted to help explain the results obtained from K3[CrxFe1-x(ox)3]·2.5H2O co-crystalisation experiments. Results showed different epitaxial growth patterns depending on the method used to immerse the seed into the growth solution. When the seeds were allowed to rest at the base of the glass vial, growth only occurred around the perimeter of the seed. Raman spectroscopic mapping and SEM-EDX results confirmed the absence of any epitaxial growth on the top or underside of the seed. However, the seeds were observed to be completely enveloped by epitaxial growth when they were affixed to glass fibres and suspended in the growth solution. The results obtained from these

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CHAPTER 6 epitaxial experiments provide great insight as to why concentration gradients in

K3[CrxFe1-x(ox)3]·2.5H2O co-crystals were consistently found to be more pronounced in some directions but not others. The results suggested that perhaps local charging effects occurring between the crystals and the glass of the vial during crystallisation inhibit crystal growth in some directions leading to preferential growth occurring around the perimeter.

It was also demonstrated that it is possible to form epitaxial crystals that have seed domains containing K3[Cr(ox)3]·2.5H2O surrounded by epitaxial growth composed of K3[Fe(ox)3]·2.5H2O. The arrangement of metal complexes in these types of crystals is essentially the inverse to what was observed to occur spontaneously from solutions that contained both complexes. The interface between the seed and epitaxial domains for these types of crystals were found to be more diffuse than crystals grown by immersing K3[Fe(ox)3]·2.5H2O seeds into K3[Cr(ox)3](aq/EtOH) saturated solutions. This result suggests that K3[Cr(ox)3]·2.5H2O crystal are slightly more soluble than K3[Fe(ox)3]·2.5H2O crystals resulting a greater partial dissolution of the former compared to the latter.

Similar epitaxial growth patterns to experiments containing only one type of seed were observed when seeds of both K3[Cr(ox)3]·2.5H2O and K3[Fe(ox)3]·2.5H2O were immersed in solutions of either K3[Cr(ox)3](aq/EtOH) or K3[Fe(ox)3](aq/EtOH). For these experiments both types of seeds were observed to have epitaxial growth. This indicates that the supramolecular interactions between the like and different complexes are similar enough to allow growth to occur on both types of crystals simultaneously.

An additional epitaxial crystal growth experiment demonstrated that a concentration gradient similar to the one observed for K3[CrxFe1-x(ox)3]·2.5H2O co-crystals resulted when K3[Fe(ox)3]·2.5H2O seeds were immersed in a saturated solution containing an equimolar ratio of K3[Cr(ox)3] and K3[Fe(ox)3]. Through the use of a saturated 1:1 solution the solubility differences between the two complexes were minimised. Therefore, the results suggest that the concentration gradient that formed was likely due to supramolecular selection as a result of a bias for K3[Fe(ox)3] rather than just fractional crystallisation. For the K3[CrxFe1-x(ox)3]·2.5H2O system the bias was likely

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CHAPTER 6 initiated by the solubility differences between the complexes while for the epitaxial system the bias was initiated by the presence of the pure K3[Fe(ox)3]·2.5H2O seed.

These results suggest that K3[Cr(ox)3] and K3[Fe(ox)3] complexes are structurally similar enough to co-crystallise but different enough such that supramolecular interactions between like complexes are slightly more favourable. The supramolecular selection which appears to have occurred for these systems has manifested differently to the selection observed for discrete molecular systems such II as [M xRu1-x(terpy)2](PF6)2, as each K3[CrxFe1-x(ox)3]·2.5H2O co-crystal batch was found to be similar i.e. all displayed a similar concentration gradient.

Four different co-crystalline 3D coordination frameworks of the type II III II [M (L)3][NaM (ox)3] were prepared through the co-crystallisation of [M (L)3]Cl2 II III (M = Ni, Ru; L = 2,2′-bipyridine, 1,10-phenanthroline) with K3[M (ox)3] (MIII = Cr, Fe) in the presence of NaCl and characterised using SEM-EDX, XRD. II 2+ Analogous cation and anion metal dilution experiments where [M (phen)3] II III 3- III (M = Ni, Ru) and [M (ox)3] (M = Cr, Fe) were co-crystallised in the presence of NaCl produced unstable rectangular prism shaped co-crystals. SEM-EDX analysis suggested the formation of metal complex salts with the general formula II III II 2+ [M (phen)3]3[M (ox)3]2·xH2O. Results suggested that [M (phen)3] complexes do not engage in supramolecular selection during the formation of

[Ni0.50Ru0.50(phen)3]3[Cr(ox)3]2 as the ratio of complexes in the solid-state was equal to the concentration in solution. Results for the [Ru(phen)3]3[Cr0.40Fe0.60(ox)3]2 3- system suggest a genuine preference for [Fe(ox)3] during the formation of this compound.

Co-crystals of all four coordination frameworks formed with a tetrahedral habit and were found to be isomorphous, crystallising in the P213 cubic space group. The unit cell parameters were found to be very similar to the parameters of the various non-diluted structures listed in the literature. Interestingly, co-crystals incorporating II 2+ II 2+ both [M (bipy)3] and [M (phen)3] complexes had unit cell dimensions slightly II 2+ smaller when compared to co-crystals without the bulkier [M (phen)3] complex. This is counterintuitive given the added bulk of the 1,10-phenanthroline ligand yet these results suggest more efficient crystal packing for A B A B [M (bipy)3]0.80[M (phen)3]0.20[NaCr(ox)3] co-crystals (M = Ni, M = Ru and vice

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versa) compared to [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] co-crystals. Furthermore, the Ni and Ru relative occupancy refinement values for all three types of co-crystals were in very close agreement to those obtained by SEM-EDX. PXRD patterns were indexed against a pattern simulated from experimental SCXRD data. No additional peaks were observed nor were the peaks significantly broader than those in the simulated pattern suggesting the presence of a single phase and a tight distribution of xsolid values.

Co-crystals of [Ni0.50Ru0.50(bipy)3][NaCr(ox)3] were found to have the same ratio of the metal complexes in the solid state that was present in solution. These results II 2+ indicate that [M (bipy)3] complexes engage in negligible supramolecular selection during co-crystallisation and therefore the solid state concentration is a random distribution of complexes, which is statistically dependant on the stoichiometry of complexes in solution. Conversely, the results for co-crystals of the formula

[Ru(bipy)3][NaCr0.60Fe0.40(ox)3] suggest that K3[Cr(ox)3] was slightly favoured over and K3[Fe(ox)3]. The results obtained from these two seemingly similar experiments strongly affirm that intermolecular interactions between complexes is a key proponent in the proposed mechanism(s) of supramolecular selection.

2+ 2+ Although both [Ni(bipy)3] and [Ru(bipy)3] have extremely similar geometric dimensions, varying only by the slightest margins, previous co-crystallisation experiments such as those that produced [NixRu1-x(bipy)3](PF6)2 co-crystals have demonstrated that even the slightest differences between complexes are recognised beyond the point of difference resulting in significant supramolecular selection.

Complex pairs in the previously reported [NixRu1-x(bipy)3](PF6)2 system interact II 2+ through six EF π-interactions. In these P213 framework structures the [M (bipy)3] complexes occupy cavities created by the 3D anionic framework and as a result II 2+ [M (bipy)3] complexes do not interact with one another. Without these supramolecular interactions occurring between pairs of complexes these minor differences go unnoticed and as a result both complexes are relatively equal with respect to their ability to template the anionic framework.

II 2+ Contrary to the arrangement of the [M (bipy)3] complexes in these 3D polymeric III 2- structures, the metal centres of the {[NaM (ox)3] }n building-blocks are linked in

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CHAPTER 6 three dimensions by oxalato ligands. It is well known in the literature that the oxalato ligands in these structures facilitate and enhance the electronic communication 3- 3- between the metal sites. Furthermore, although both [Cr(ox)3] and [Fe(ox)3] have very similar geometric dimensions, the relative structural change imparted when one III 3- metal centre is substituted for another is greater for [M (ox)3] complexes than II 2+ [M (bipy)3] due to the smaller size of the oxalato ligand and consequently the III 3- [M (ox)3] complex. It is possible that these factors amplified the minor structural differences between the complexes and consequently the ability for complexes to engage in the molecular recognition process involved during the formation of the anionic framework. Overall, the results obtained for this system imply that however 3- minor the differences between the complexes, it seems that [Cr(ox)3] was slightly 3- more energetically favoured over [Fe(ox)3] during the formation of the

[Ru(bipy)3][NaCrxFe1-x(ox)3] metal-organic framework.

II 2+ II 2+ The [M (bipy)3] : [M (phen)3] ratio in [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] and [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] co-crystals was found to be 4:1. This ratio was found to be consistent despite co-crystallising solutions containing up to a II 2+ II 2+ four-fold excess of [M (phen)3] compared to [M (bipy)3] . These results indicate II 2+ the formation of co-crystals with a ca. 20% threshold for [M (phen)3] is allowed in the framework structure. Interestingly, far fewer co-crystals were observed to form in II 2+ experiments with a substantial excess of [M (phen)3] . For each experiment neither

[Ni(bipy)3][NaCr(ox)3] nor [Ru(bipy)3][NaCr(ox)3] crystals were found to form from either system and all crystals analysed were found to contain both nickel and ruthenium.

II 2+ Through SCXRD it was found that at full occupancy of [M (phen)3] each complex II 2+ would overlap with six others. Hence, only 14% of the [M (phen)3] molecules could be accounted for in the orientation modelled in the refinement. However, since both the SEM-EDX results and the occupancy refinement of the MII site indicated a II 2+ [M (phen)3] concentration of ca. 20%, another orientation or orientations with partial occupancies totalling 0.06 must also be present. The carbon atoms of the complexes in these orientations were not observed and subsequently not modelled as at 6% occupancy would have electron densities less than half of those of hydrogen atoms.

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II 2+ Most interestingly, it was discovered that the [M (phen)3] molecules in both II 2+ structures exhibited the opposite chirality to the [M (bipy)3] complexes and to the 2- metals in the {[NaCr(ox)3] }n helical anionic framework such that single crystals A B had the general formula Λ-[M (bipy)3]0.80Δ-[M (phen)3]0.20Λ-[NaCr(ox)3]. These II 2+ results indicate that only the [M (bipy)3] complexes act as a template for the II 2+ formation of the anionic framework. The results suggest that [M (phen)3] II 2+ complexes are similar enough to [M (bipy)3] complexes to occupy the cavities formed by the framework but too large and bulky to template the anionic framework to form with the dimensions observed. The heterochiral structure of these co-crystals II III is especially novel as [M (L)3][NaM (ox)3] single crystals have historically been known to only form homochiral structures.

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CHAPTER 7: Directions for future research

Using the methods discussed within this thesis, the scope for synthesising single co-crystals that are capable of displaying tunable properties is infinite. For example, analogous experiments to those discussed within this research could be undertaken where experimental conditions such as temperature, solute concentration or solvent are altered so that a better understanding of the thermodynamic and kinetic mechanisms governing co-crystallisation could be gained. Similarly, the scope for investigating the limitations of supramolecular selection is extremely broad as only a few select systems were analysed within this work in order to highlight this remarkable newly discovered phenomenon. The prevalence of supramolecular selection could be investigated for by performing co-crystallisation experiments involving other known systems. However, in regards to the overall objective of this work i.e. engineering novel co-crystalline materials with potentially tunable properties and in light of the results obtained, two avenues of research are of particular interest. The first is the use of heteroleptic metal complexes in co- crystallisation experiments and the second is the design of new crystallisation techniques to intentionally form co-crystals that contain concentration gradients.

II 2+ II Experiments where [M (bipy)3] (M = Ni, Ru) was co-crystallised with III 3- III [M (ox)3] (M = Cr, Fe) in the presence of NaCl produced single co-crystals of the II III II 2+ 3D coordination framework [M (bipy)3][NaM (ox)3]. However when [M (phen)3] II II 2+ (M = Ni, Ru) was used in lieu of [M (bipy)3] only unstable co-crystals suspected II III to be the metal complex salt [M (phen)3]3[M (ox)3]2·xH2O formed. It would therefore be interesting to observe if the 3D coordination framework or the metal II 2+ complex salt formed when heteroleptic complexes of [M (bipy)2(phen)] or II 2+ III 3- [M (bipy)(phen)2] are co-crystallised with [M (ox)3] in the presence of NaCl. II 2+ II 2+ Experiments that involved both [M (bipy)3] and [M (phen)3] produced single co-crystals of the heterochiral 3D coordination framework A B Λ-[M (bipy)3]0.80Δ-[M (phen)3]0.20Λ-[NaCr(ox)3], where the threshold of II 2+ [M (phen)3] complexes was found to be ca. 20%, despite solutions containing a II 2+ four-fold excess of [M (phen)3] . Should co-crystals of the 3D coordination II 2+ II 2+ framework form when either [M (bipy)2(phen)] or [M (bipy)(phen)2] are

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II 2+ substituted in solution for [M (phen)3] , it would be curious to see if the thresholds II 2+ for the heteroleptic complexes are larger than that of [M (phen)3] given their reduced bulk. It would also be interesting to see if heterochiral or the traditional homochiral structures formed.

Throughout this research, two systems were identified as having spontaneously formed co-crystals that contained intracrystal solid-state concentration gradients; II II co-crystals of [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (M = Fe, Ni, Cu) and

K3[CrxFe1-x(ox)3]·2.5H2O. Co-crystals that contain concentration gradients have the potential to display a continuum of concentration dependant properties. Furthermore, co-crystals that contain concentration gradients defy the generally accepted definition needed to classify a solid as a crystal:

“a homogenous solid formed by a repeating, three-dimensional pattern of atoms, ions, or molecules”.

II II For example, co-crystals of [M (terpyOH)2]x[Ru(terpy)2]1-x(BF4)2 (M = Fe, Cu) II were found to adopt the [M (terpyOH)2](BF4)2 phase when xsolution = 0.50 yet adopt the [Ru(terpy)2](BF4)2 when xsolution = 0.05. In each case, the concentration gradient that spontaneously formed was relatively modest. However, if experiments were designed so that the concentration in solution was controlled and constantly changing to yield co-crystals with concentration gradients ranging from 0.05-0.50 of II [M (terpyOH)2](BF4)2 it may be possible to form a multiphase crystal. In this scenario it would be very intriguing to analyse the crystal structure of these co-crystals. Would the phase differences between the zones in such a crystal be gradual or abrupt and how would these crystals be categorised? By manipulating the concentration of the complexes during co-crystallisation it would also be possible to grow co-crystals containing concentration gradients that would otherwise not spontaneously form with concentration gradients. The ability for a single crystal to display zone specific properties, such as phase, spin state, magnetism and chirality would be a significant advancement in the engineering of multifunctional crystalline materials.

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240

APPENDICES

APPENDIX A

APPENDIX A: The use of SEM-EDX for quantitative analysis

Over the past few years members of the McMurtrie group have quantitatively characterised the co-crystals resulting from various co-crystallisation experiments ranging from simple binary homoleptic systems to more complex heteroleptic and different ligand combinations. Single crystal SEM-EDX was the characterisation technique used to quantify the mole fractions of the various metals and by extension the metal complexes in the co-crystals.

The EDX technique relies upon a high energy beam (in this case a beam of electrons) to eject an electron within the sample from an inner atomic shell into an excited state thereby creating a hole. This hole is then filled by an electron from an outer atomic shell of higher energy; and the difference between the two energies of the respective shells can be released as measurable X-rays. The number/energy of emitted X-rays observed for any given element is different because each atomic structure is unique. The result is a set of characteristic patterns of spectral peaks for each different element, which can then be used for elemental analysis.

As mentioned throughout the body of this thesis SEM-EDX is a surface technique.

The thickness of the material that is analysed i.e. the X-ray excitation depth (Rx) can be calculated using Anderson’s equation. 0.064 (E1.68 - E1.68 ) R  0 c x 

Rx = range (depth) over which the particular X-ray line is produced (µm)

E0 = incident beam energy (kV)

Ec = critical excitation energy for a particular X-ray line (KeV)  = sample density (g/cm3)

So for an instrument set at an incident beam energy (E0) of 20 keV to analyse a sample with a density of 1.5 g/cm3 the value of the excitation depth (depth of X-ray production) for the co-crystals discussed in this thesis is 4.8-5.6 µm.

241

APPENDIX A

For elemental analysis to be considered quantitative, several aspects of the technique must be tuned in favour of the samples being analysed. The first is peak overlap, which is a common concern with any technique. EDX distribution functions rely on the mathematic integration of spectral peaks and the fitting of those peaks to theoretical profiles in order to generate an elemental composition. Therefore, any peak overlap or even lack of baseline resolution could have the potential to produce unreliable data. An example that is particularly noteworthy for this project is the overlap of Ru and Cl peaks and to a lesser extent Ru and P peaks, although peaks of any element have the possibility to overlap with another, particularly if that element has many observable bands (e.g. iodine has peaks that range from 3-5 keV).

As mentioned previously, spectral bands are a result of the perturbation of the atom’s electronic structure that is caused by a focused beam of high energy electrons. Holes that are created in the innermost electron shell (principal quantum number, n = 1) give rise to either K or Kβ peaks, however those created in outer shells (n = 2 or 3) generate lower energy L, Lβ and M, Mβ peaks. The  and β represent the number of shells, one or two respectively, traversed by the electron filling the hole. Ideally, the perfect EDX analysis is one that uses only baseline-resolved high energy K lines. In practice however, this is rarely possible. The instrument used throughout this research was capable of producing accurate standardised spectra within the range of 0-10 keV and therefore throughout in this project, it was necessary to rely upon Ru

L and Lβ lines because the K peaks were well beyond the capabilities of the instrument (19.3 keV). Issues regarding the accuracy and reproducibility of this analysis technique using Ru L and Lβ excitation lines have already been addressed during the candidate’s Honours project and were shown to be accurately quantitative for samples of this type, providing the standardisation protocol was followed. Other metals present in co-crystals analysed, (e.g. Fe, Co, Ni, Cu), have observable K excitation lines within the spectral range specified.

In addition to the spectral hurdles discussed above, an unexpected complication emerged when analyses of single co-crystals generated mass percent totals that were much higher or lower than 100% and/or yielded stoichiometrically invalid data. This is because a large proportion of the elements that constitute these materials are

242

APPENDIX A relatively light (C, N, O, F and P). These light elements have observable K peaks at or below 2 keV, are prone to absorption problems, which can manifest when the specimen geometry is improperly aligned with the detector. Although it is possible to correct for absorption, the accuracy of the analysis of low energy X-ray peaks remains questionable. A remedy for this, which was employed in the project, was to physically tilt the sample into the correct position. This is illustrated using the EDX data shown in Figure A1 taken from the same area on the same co-crystal, which was grown from a solution containing a 1:1:1:1:1 ratio of 2+ 2+ 2+ 2+ 2+ [Fe(phen)3] :[Co(phen)3] :[Ni(phen)3] :[Cu(phen)3] : [Ru(phen)3] . Using the

At% II equation x  M to convert the absolute At% values to relative ratios (x) the At% II M formula of this co-crystal and every other co-crystal analysed from this batch was found to be [Fe0.20Co0.20Ni0.20Cu0.20Ru0.20(phen)3](PF6)2 (within ± 0.02).

243

APPENDIX A

(a) [Fe0.20Co0.20Ni0.20Cu0.20Ru0.20(phen)3](PF6)2 at 0° stage tilt

Raw At% Fe:Co:Ni:Cu:Ru Ratio (Fe) 0.38 0.21 (Co) 0.38 0.21 (Ni) 0.36 0.20 (Cu) 0.37 0.20 (Ru) 0.35 0.19 Σ(MII) 1.84 Raw At% F:P Ratio (F) 21.41 6.10:1 (P) 3.51 P:(ΣMII) Ratio 1.91:1

(b) [Fe0.20Co0.20Ni0.20Cu0.20Ru0.20(phen)3](PF6)2 at -5° stage tilt

Raw At% Fe:Co:Ni:Cu:RuRatio (Fe) 0.44 0.20 (Co) 0.47 0.21 (Ni) 0.43 0.20 (Cu) 0.44 0.20 (Ru) 0.42 0.19 Σ(MII) 2.20 Raw At% F:P Ratio (F) 19.58 5.55:1 (P) 3.53 P:(ΣMII) Ratio 1.60:1

(c) [Fe0.20Co0.20Ni0.20Cu0.20Ru0.20(phen)3](PF6)2 at +5°stage tilt

Raw At% Fe:Co:Ni:Cu:RuRatio (Fe) 0.33 0.20 (Co) 0.35 0.21 (Ni) 0.33 0.20 (Cu) 0.35 0.21 (Ru) 0.31 0.19 Σ(MII) 1.67 Raw At% F:P Ratio (F) 21.98 7.35:1 (P) 2.99 P:(ΣMII) Ratio 1.79:1

Figure A1: EDX spectra collected from the same area on the same co-crystal with the formula [Fe0.20Co0.20Ni0.20Cu0.20Ru0.20(phen)3](PF6)2 that was grown from a solution containing a 1:1:1:1:1 ratio 2+ 2+ 2+ 2+ 2+ of [Fe(phen)3] :[Co(phen)3] :[Ni(phen)3] :[Cu(phen)3] : [Ru(phen)3] at stage tilts of (a) 0°, (b) -5° and (c) +5°. The Raw At% and the normalised Fe:Co:Ni:Cu:Ru ratios are shown. The Raw At% values for F and P and the F:P and P:ΣMII ratios are also shown.

244

APPENDIX A

Because the co-crystals are analogues of known compounds, it is possible to use the known chemical stoichiometry to check the validity of the data and the degree of tilt needed. For example, for the sample whose EDX data are shown in Figure A1 it is possible to use the F:P and P:ΣMII ratios. For the co-crystal shown in Figure A1 the F:P and P:ΣMII ratios should be 6:1 and 2:1 respectively. However, the data shown in Figure A1 illustrate that these ratios can change depending on the tilt of the sample relative to the detector. More importantly to this thesis, what this data also show is that despite the tilt, the relative ratios of the transition metals (x) remain largely unaffected. This suggests that providing the data are within reasonable limits with respect to stoichiometry such as the F:P ratio, the relative values obtained are reliable and therefore are valid for quantitative use.

245

APPENDIX B

APPENDIX B: EDX analysis of the residues obtained by the evaporation of the II 2+ mother liquors for co-crystallisation experiments involving [M (L)3] and III 3- [M (ox)3]

The depletion state of the various solutes at the time of co-crystal harvest is an estimation of experimental yield and can be very crudely gauged in two ways; visual inspection of the coloured solution and from EDX measurements taken from the powder residues obtained by evaporating the solvent from the mother liquors. Initially the solutions of all experiment types were intensely coloured due to the 2+ 3- presence of [Ru(L)3] and [Cr(ox)3] both of which are highly absorbing in the visible region. As these species are consumed to form co-crystals, their concentration in solution depletes, which according to Beer’s Law translates to a decrease in absorbance. After 13 days, the mother liquors for the

[Ni0.47Ru0.53(bipy)3][NaCr(ox)3] system (experiment type 1) and the

[Ru(bipy)3][NaCr0.58Fe0.42(ox)3] system (experiment type 2) were nearly colourless. 2+ It is interesting that the initial [Ru(bipy)3] concentration for the latter was double that of the former, yet the colours of the mother liquors at the time of crystal harvest were very similar. These observations suggest that after 13 days, a large proportion of the highly absorptive complexes had been consumed. The appearance of the mother liquors for the remaining experiments, i.e. for experiments involving II 2+ [M (phen)3] complexes, were visually very similar and still intensely coloured. These observations suggest that these systems form less solid material (i.e. crystals) II 2+ than those that do not involve [M (phen)3] and thus a large proportion of material remains in solution.

The Ni:Ru or Cr:Fe ratios calculated from the EDX measurements from these powdered residues cannot easily be used to gauge a co-crystallisation’s completion. These ratios are only valid if one of the metals in the ratio is not detected (i.e. 1:0 or 0:1) or if the exact weights of the starting materials, co-crystals and the residue are known. The latter condition must be met, as even a 0.50:0.50 initial concentration can yield a 0.50:0.50 final concentration when only a small number of crystals are formed with xsolid values ≠ 0.50. Weighing the crystals would unavoidably involve the loss of some of the mother liquor, which would impact on the final weight of the residue. Given the co-crystallisation experiments are done on a very small scale (ca.

246

APPENDIX B

20 mg), this loss would be a significant source of random error. A alternate method is III III III to use the known 3:1 K:M ratio in K3[M (ox)3] starting material(s) (M = Cr, Fe) as a basis. Since potassium is not consumed during co-crystallisation, its concentration in the mother liquor remains constant throughout the entire III experiment. Therefore, at t0 the EDX values reflect the 3:1 K:M ratio. As co-crystallisation progresses and MIII is consumed to form co-crystals, the amount of MIII gradually depletes as does its concentration relative to potassium. Theoretically, at 100% co-crystal yield, the EDX of the powder residue would show a dominant potassium peak but no peaks attributed to chromium and/or iron. Representative EDX spectra of the residues obtained by evaporating the mother liquors from all six experiment types are shown in Figure B1.

(a) Experiment type 1 Complexes in solution 2+ Cation(s): [Ni(bipy)3] 2+ [Ru(bipy)3] 3- Anion(s): [Cr(ox)3]

(b) Experiment type 2 Complexes in solution 2+ Cation(s): [Ru(bipy)3] 3- Anion(s): [Cr(ox)3] 3- [Fe(ox)3]

247

APPENDIX B

(c) Experiment type 3 Complexes in solution 2+ Cation(s): [Ni(phen)3] 2+ [Ru(phen)3] 3- Anion(s): [Cr(ox)3]

(d) Experiment type 4 Complexes in solution 2+ Cation(s): [Ru(phen)3] 3- Anion(s): [Cr(ox)3] 3- [Fe(ox)3]

(e) Experiment type 5 Complexes in solution 2+ Cation(s): [Ni(bipy)3] 2+ [Ru(phen)3] 3- Anion(s): [Cr(ox)3]

248

APPENDIX B

(f) Experiment type 6 Complexes in solution 2+ Cation(s): [Ni(phen)3] 2+ [Ru(bipy)3] 3- Anion(s): [Cr(ox)3]

Figure B1: SEM-EDX spectra measured from the power residues which were obtained by evaporating the mother liquors to dryness from experiment types 1-6. The complexes that were in solution are listed as insets in each spectrum.

It is serendipitous that for all six systems, the potassium peak (highlighted in yellow) does not overlap with any other signals. Since co-crystals from each experiment were harvested after 13 days and given that experiments seldom achieve absolute completion, this method may be a useful way to rank the various experiment types according to their degree of completion. Depending on the type of experiment, the K:MIII ratio is calculated by dividing the atomic percentage (At%) for potassium by the At% for MIII (chromium alone or chromium and iron combined). Table B1 lists the experiment types in descending order according to the mean found K:MIII ratio. The standard deviations are also shown.

249

APPENDIX B

Table B1: Ranking of experiment systems from most depleted to least depleted according to the K:MIII values deduced from SEM-EDX data of the powder residues. The co-crystal formula are shown (where known).

III Experiment system Co-crystal formula (where known) xˉ ± s (K:M ) from residue at t13days

2 [Ru(bipy)3][NaCr0.58Fe0.42(ox)3] (25.1 ± 6.7):1

1 [Ni0.47Ru0.53(bipy)3][NaCr(ox)3] (13.9 ± 1.6):1

6 [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3] (4.7 ± 0.8):1

5 [Ni(bipy)3]0.77[Ru(phen)3]0.23[NaCr(ox)3] (4.4 ± 0.6):1

2+ Cation: [Ru(phen)3] 4 (3.6 ± 0.4):1 3- 3- Anions: [Cr(ox)3] , [Fe(ox)3] 2+ 2+ Cations: [ Ni(phen)3] , [Ru(phen)3] 3 (3.2 ± 0.2):1 3- Anion: [Cr(ox)3]

The information presented in Table B1 suggests that after 13 days, experiment types III 3- 1 and 2 had the least amount of [M (ox)3] remaining in the respective mother liquors as indicated by their large K:MIII ratios. By comparison, the systems II 2+ III involving [M (phen)3] have the smallest K:M ratios. This suggests that a greater proportion of co-crystals by weight (experimental yield) are formed in systems not II 2+ involving [M (phen)3] . In other words, these results imply that the inclusion of II 2+ [M (phen)3] hinders the progress of the experiment. This conclusion is in agreement with the visual assessment regarding the colour intensities of the various mother liquors at the time of co-crystal harvest.

As mentioned earlier this method is a crude estimation of co-crystallisation yield. This is partly because of the errors associated with measuring small amounts of material and software fitting errors for very small EDX peaks both of which are issues when measuring these residues. The standard deviations shown in Table B1 encompass all of these errors and therefore the system with the least amount of MIII remaining in solution and hence the largest mean K:MIII also has the greatest standard deviation; the opposite is true for the system with the smallest K:MIII ratio. Because of the standard deviations, the relatively small K:MIII values for systems II 2+ involving [M (phen)3] overlap. Therefore, this table divides the experiment types II 2+ into two groups, those that involve [M (phen)3] and those that do not rather than ranking them in a specific order.

250

APPENDIX C

APPENDIX C: PXRD of K3[CrxFe1-x(ox)3]·2.5H2O co-crystals

PXRD: K3[CrxFe1-x(ox)3]·2.5H2O co-crystals

K3[Fe(ox)3]·2.5H2O

xsolution = 0.10

xsolution = 0.50 Counts

xsolution = 0.90

K3[Cr(ox)3]·2.5H2O

5 10 15 20 25 30 Position [ 2θ (Co)] III III Figure C1: PXRD of K3[M (ox)3]·2.5H2O K3 (M = Cr, Fe) and [CrxFe1-x(ox)3]·2.5H2O co-crystals (x = 0.90, 0.50, 0.10).

251

APPENDIX D

APPENDIX D: Literature SCXRD refinement data for [Fe(terpyOH)2](BF4)2·H2O, [Cu(terpyOH)2](BF4)2·H2O (CAPXUN, CAPYIC) and experimental data for [Ni(terpyOH)2](BF4)2·H2O and [Ru(terpy)2](BF4)2·H2O

=

) + o I (all) ( 2 2 O 2  H wR

·

2 ) 4 08 Ru ) = [ 8 o and I

F ( ) 2

o (BF × 0. 

]

F 2 ) ) (

) OB 2 2 6  ( ( (3)

N

24 > 2



a K H o

/

1 340.17 × F 30

Ru(terpy 4 [ C 759.26 173(2) Mo Tetragonal I 12.3927 12.3927 39.2667(12) 90 90 90 6030.5 4 red plate 0. | | for o

F | O 2  H ||/ · c 2 ) being derived from ) o F 4 |

F ( – Ni 2 8 | (BF  o ] F

2 2 F )

||

B

3



O 6 ) with

o b b

N 1 =

8 F R 24

(

 2

K (terpyOH) H 1  30 2 )/3.

Ni 0.800, 0.810 1/ 2 [ C 748.8 173(2) Mo Monoclinic P 8.7415(4) 8.9773(4) 19.9816(9) 90 99.063(4) 90 1548.48(12) 1.606 2 brown Rectangular prism 0.470.41 × × 0.17 0.719 0.171, 0.883 8181(0.0329 7335 430 0.0509 0.1113 0.02,3 0.044(14) 1.085 - c F

+ 2 +

O 2 2 o H F · 2 ) 4 = (

P Cu 8 (BF ], ], ] F

2 P 2

B B )] considered observed.

3

I ( +

O

2 

6 )

N

P a a

> 2 24

 A

(terpyOH)

K I H 1

30 2 53.71 Cu 0.66, .56 Reflection weights used were ) + ( [ CAPYIC C 7 293 Mo Monoclinic P 8.806(2) 9.047(1) 20.163(4) 90 98.38(1) 90 1589.2(5) 1.57 2 Blue/green Rectangular prism 0.774 No Correction 3058(0.013) 2972 155 0.051 0.068 – 1.27 - 2 o F (

2 O  2 H · 2 ) = 1/[ 4

w Fe Reflections with [ 8 (BF

] b F 2 2 .

B 3 1/2 where where

)

2 O

6 F

9) 1/2

N

)] considered observed. w a a

I ]} 24 (1) Σ (  2

) K (terpyOH) / H  2

2 c

30 ¯ 1

Δ Fe 1.11, 0.081 F [ CAPXUN C 746.00 293 Mo Triclinic P 8.668(5) 9.278(6) 20.214( 78.80(4) 78.24(4) 87.93(3) 1561 1.59 2 purple Rectangular prism 0.570 No correction 5414(0.012) 4174 149 0.053 0.081 – 1.95 - ( > 3 w

w I Σ [

 = (

]/

2 ] ]

)) ) 3 1

- - 2 I with with [ c (

Rw Å

F 

. -

] ] 1 –

3 1/2 - [e

Code -

]

) 2 > 2 ) [mm 2

o

 ) I int

o F ( K ]

I R (

3

-

(

]

] w ] 2 [g cm[g min,max ° [g [g mol ° [

° [Å [K] [ [Å] [Å] [ c [Å] var ind obs [ 1  Reflections (Mo min,max



CSD Ref Formula M T Radiation Crystal System Space Group a b c α β γ V D Z Colour Habit Dimensions [mm]  T N N N R wR B A, parameterFlack GoF  a (0.04 {

252 dfsfhjdjgdjfgjhfjkhdkdhkdgkhdgkdklhs Hdjhdjgdjfjfjdkghkgdkgkgjdkjgkjgdgljdlj APPENDIX E

II APPENDIX E: SCXRD refinement data for [M (terpyOH)2]x[Ru(terpy)2]1- II x(BF4)2·H2O (M = Fe, Ni, Cu) co-crystals

=

O 2 w H · 2 ) 4 where where (BF x

- 1

] 1/2 2 ]} 0.50 2 ) 2 c Ru F ( 0.50 w

[ Cu [Ru(terpy)

 07 8 x ] ]/ F

2 2 2 )

) 2 × 0. B

c 2

F

O 10

6 , 1 ,

0.817 –

4

N

0.0281 , 2

( , o 24 × 0. ×



(terpyOH)

F K H 05 1 (

40 30 olumnar prism 2

w Cu 0.710 [ [ C 756.47 173(2) Mo Monoclinic P 8.7360(2) 8.9198(2) 19.8678(4) 90 98.929(2) 90 1529.40(6) 1.643 2 Dark red C 0. 0.703 0.94965 6813 5859 427 0.0491 0.0914 0.0 0.37(2) 1.009 - 

= { O

2 (all) ·H 2 2 ) 4 wR (BF x -

1 0 ] 2 ) and 0.4 o F ( Ru 0  0.6

> 2 Ni

8 o [Ru(terpy) 42 F x 2 F ]

2 )

B

× 0.

2.2

| | for O o 6 , 1 , 0.976

F

N

| 0.0275 ,

( 3  24



K ||/ H 5, 1 c

120.15 × 93832 30 2

F 1.045 | [Ni(terpyOH) C 753.00 173(2) Mo Monoclinic P 8.7473(2) 8.91280(10) 19.9016(4) 90 99.3919(19) 90 1530.79(5) 1.643 2 Red Rectangular prism 0. 0.664 0. 6870 6226 429 0.0487 0.1145 0.0 0.20(2) 1.011 -

– | o

F O || 2  ·H 2 ) 4 1 = R (BF x -

1 0 ] 2 0.4 Ru

0 0.6 )/3. 2

c Fe 8 F [Ru(terpy) 35 F x 2 ]

2 )

B + 2

× 0.

2

2.2

o

)

O F ) ) 2 21

6 ( (6) 1 , 4 2 2 ( (

N )] considered observed.

0.0154 = ( = I

3 26 ( 1, purple 24 × 0. × (

 18 P

 K H 8646 00

], ], 20 30 ¯ 1

0.870, 0.791 P [Fe(terpyOH) C 751.30 173(2) Mo Triclinic P 8.657 9.10 20.17 79.726(5) 78.315(5) 88.370(5) 1531.60 1.639 2 Dark Rectangular prism 0. 0.593 0.9 6808 5939 498 0.0468 0.1009 0.0 – 1.046 - > 2 B

I +

2 )

] ] P

)) 3 1 - - I with [

A (

Å



-

] ] 1

3 - [e ) + ( -

) > 2 2 ) [mm

o

 I int

( F K

]

R ( a 3

-

( 2

]

]

] 2 [g cm[g min,max ° a  [g [g mol °

° [Å [K] [ [Å] [Å] [ c [Å] var ind obs [ Reflections 1  (Mo min,max

Formula M T Radiation Crystal System Space Group a b c α β γ V D Z Colour Habit Dimensions [mm]  T N N N R wR B A, parameterFlack GoF  a 1/[

Shdjhdgjgjjkajkarkarykyrk 253 hdsjhdtgjrjyrajkyrkyrkyarkyk

APPENDIX F

APPENDIX F: Additional SCXRD refinement data for co-crystals of [Ni0.50Ru0.50(bipy)3][NaCr(ox)3], [Ni(bipy)3]0.80[Ru(phen)3]0.20[NaCr(ox)3] and [Ni(phen)3]0.20[Ru(bipy)3]0.80[NaCr(ox)3]

] 3

80 [NaCr(ox) 0. 0.80 Ru ] 3 12 O 0 0.2 [Ru(bipy) NaNi 0 6

0.2 )

] 3

) ) ) ) CrN

5 4 2 24

(3) (3) (3) (4) (1 (1 (1 H 6 7 6

(phen) 60 41 28 48 12 88 77

37.20

Ni [ C 15.4642(3) 3698.17(12 Λ Δ 2.0 2.06 1.962(3) 1.96 2.3 2.321(4) 81. 88.70(15 83. 73.9 54. 65. 53.53 45. 1.41 1.32 1.50 30.40 0

] 3

20 [NaCr(ox) 0. 0 0.2 Ru ] 3 12 O 0 0.8 [Ru(phen) NaNi 6 80 ) 0.

]

3 ) ) CrN

) ) 4 3 24 4 4

68(15 (4) (4) ( ( (4) (4) (15) (15) (1 (1 H 1 3 0 8 2 5 1 8 6

(bipy) 62 68

37.20

Ni [ C 15.4664(4) 3699. Λ Δ 2.07 2.08 1.96 1.9 2.31 2.34 80.4 89.5 83.7 73. 52.81 67.19 53.57 45.7 1.41 1.31 1.51 30.40 0

] 3

0.50 Ru 12 O ][NaCr(ox) 3 0.50

(bipy) NaNi 0

6 (16) 0.5

(7) 3 CrN

Ru (2) (2) (3) (2) (9) (8) (7) 24 8 7 7 8 6 1 9

0.50 H 50 36

Ni [ C 15.49981 3723.7 Δ – 2.074(2) 2.06 1.96 1.969(2) 2.32 2.33 78.6 – 83. 74.1 49.6 – 53.24 45.83 1.41 1.31 1.50 30.41 314.5

N2′) N2) O4) O2)     II II M Cr M Na

   

] 3

(N1 (O1

(N1 (O3

------2 2 2 2+ 2+ 2+ 2 2 2 2+ 2+ 2+ ] ] ] ] ] ] ] ] ] ] ] ] 3 3 3

3 3 3 3 3 3 3 3 3

2+ ]

3

(ox) (ox) (ox)

(ox) (ox) (ox) ]

3 N1 N2 O3 O4 (bipy) (phen) (bipy) (phen) (bipy) (phen) (L) Cr Cr Cr O1 O2 Cr Cr Cr (Oh: 1.22)  – II II II II II II II

– – – – [Å II II [Å]

Na Na Na Formula a V Chirality [M [M Bond lengths [Å] M M Cr Cr Na Na Bite angles [°] (Oh:90°) [M [M [Na [ Twist angles [°] (Oh: 60°) [M [M [Na [ s/h [M [Na [ Helix angles [°] Void[Å volume

254