Perkins Niu 0162D 13222.Pdf
ABSTRACT
SYNTHESIS AND PROPERTIES OF LANTHANIDE METAL-ORGANIC FRAMEWORKS AND LANTHANIDE-METALLOID COMPLEXES: STRUCTURAL DETERMINATION, PHOTOLUMINESCENCE, AND APPLICATIONS
Timothy Perkins, Ph.D. Department of Chemistry and Biochemistry Northern Illinois University, 2018 Chong Zheng, Director
Materials synthesis is a field at the intersections of chemistry and physics with wide- ranging applications. There is a rich diversity of techniques to develop novel materials, but very little fundamental understanding of the mechanisms that drive the formation of solids, leading to an inability to predict a synthesis for a material with targeted properties. Solvothermal synthesis has garnered much attention in the field due to its relative predictability by combining solution- phase dynamics with reactive inorganic precursors. By incorporating composition-guided organic chemistry, which often benefits from predictable properties, metal-organic frameworks (MOFs) synthesized solvothermally have emerged among the most rationally designed solids in modern science.
MOFs are a class of crystalline materials composed of metal-centers linked by organic ligands, forming large, porous networks. Structures, thus some properties, can be predicted given motifs for previously determined metal-center geometries and ligand-bonding environs. Further, targeted properties can be chemically tuned via optimization of the ligand and/or metal. Early efforts in the field resulted in the intriguing materials that failed to be commercially viable due to stability issue. Metal-organic frameworks using lanthanide metal-centers (Ln-MOFs) are thought to increase thermodynamic stability of the material and present unique electronic properties such as photoluminescence.
The projects presented herein focus on investigating the properties and stability of lanthanide metal-organic frameworks with a naphthalene-based ligand. To be a commercially viable material, among other things a MOF must be stable in addition to having practical properties. The increased complexity in both the accessible geometries and electronic properties of lanthanides relative to light transition metals makes this work largely exploratory. Novel, isostructural cerium, neodymium, and europium Ln-MOFs comprised of two-dimensional sheets of metal-carboxylate centers bridged by naphthalene were synthesized and photoluminescence properties analyzed. The series of Ln-MOFs studied show they have robust photoactivity that may be exploited in small molecule or ion sensing.
Compound [Ce(NO3)(NDC)]n was found to be stable under basic and acidic aqueous conditions, but not thermally stable to 400°C. Small aromatic molecules were screened against
[Nd(NO3)(NDC)]n and fluorescence quenching shown to be correlated to spectral overlap, with significant signal quenching of benzene, but no observed selective change in excitation or emission wavelengths. Further, the compound was found to be stable to 300°C in open air. In particular, compound [Eu(NO3)(NDC)]n was shown to be highly fluorescent in water and is readily quenched by trace concentrations of hazardous industrial by-product chromic acid. These investigations represent a broad effort to characterize Ln-MOFs in hopes of guiding the development of similar materials that exhibit robust chemical and thermal stability and relevant properties. Isoreticular synthesis is generally, but not exactly, an appropriate tool for replicating the synthesis with naphthalene-based ligands but different lanthanide metals. Procedurally altering the reported successful synthetic conditions with lanthanide metals is highly likely to produce isostructural and comparably stable compounds that exhibit unique electronic properties.
Solvothermal synthesis using thiourea as a reactive solvent was also shown to produce unique lanthanide-metalloid complex germanium (II) sulfide doped lanthanum (III) hydroxide.
The complex was found to photocatalytically degrade dye methylene blue in water under UV irradiation. While, not as efficient as known photocatalyst anatase titania, it represents a new class of lanthanum oxides doped with small band gap semiconductors that may be more easily optimized for photocatalytic processes than investigations on titanium dioxide have proven to be. Such intercalated lanthanum oxides may even have other relevant photo-driven applications, such as light harvesting or water-splitting. NORTHERN ILLINOIS UNIVERSITY DE KALB, ILLINOIS
AUGUST 2018
SYNTHESIS AND PROPERTIES OF LANTHANIDE METAL-ORGANIC FRAMEWORKS
AND LANTHANIDE-METALLOID COMPLEXES: STRUCTURAL DETERMINATION,
PHOTOLUMINESCENCE, AND APPLICATIONS
BY
TIMOTHY PERKINS © 2018 Timothy Perkins
A DISSERTATION SUBMITTED TO THE GRADUATE SCHOOL
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE
DOCTOR OF PHILOSOPHY
DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY
Doctoral Director: Chong Zheng ACKNOWLEDGEMENTS
I am eternally grateful to my advisor, Dr. Chong Zheng. Under his tutelage, he gave me freedom to make mistakes, to learn, and ultimately to earn my successes. His willingness to put so much trust in me and give me latitude over the lab has provided me a solid foundation in successfully designing and executing relevant research. His support is evidenced in the (several) organizational overhauls of the laboratory he has stoically endured, and the collaborative trips to both Beijing and Shanghai we took. I would like to thank Dr. Fuqiang Huang of Peking University and the Shanghai Institute of Ceramics for extending the invitation to use their excellent facilities, and especially his students Jianqiao He and Xian Zhang who taught me so much and were the senior colleagues I did not have at Northern Illinois University.
I would also like to extend my gratitude to the members of my committee: Dr. Victor
Ryzhov, Dr. Lee Sunderlin, and Dr. Zhili Xiao. Their support and input have been critical not only in helping me shape my work into a completed dissertation, but for years prior. Dr. Ryzhov often acted as a second advisor and has provided me with guidance without which I could not have succeeded. I would very much like to thank Dr. Sunderlin for letting me stop by his office unannounced for many stimulating conversations, as well as lending me tools from his lab more times than he knows. I would be remiss if I did not acknowledge the faith in me Dr. Zhili Xiao placed by recommending me to a colleague at Argonne National Laboratory, which gave me access to some of the best facilities available and exposed me to a professional safety culture I have strived to implement at NIU. iii My group members James O’Sullivan, Sura Ginting, and Crystal Ferels have always been available to lend a hand and bounce around ideas. My undergrad Noel Amaro was a delight to work with and often enabled me to be in two places at once.
Aaron Sturtz, the laboratory mechanic, has helped me repair and modify so much equipment he has surely saved the university more than his salary, and saved me countless hours.
The electrical expertise of Mike Figora probably saved me from getting shocked a few times, and
I couldn’t have upgraded our ovens and furnaces without him. I am also sincerely grateful for all the support Dr. Taesam Kim, instrumental specialist, has provided our research lab over the years.
He is not only the first line of defense when troubleshooting but an excellent teacher.
I need to give a special thank you to my parents, Dennis and Cindy Perkins, who have unconditionally supported me at every step. Finally, I thank Katherine Didier, who has been my best friend and companion, and has always been a source of encouragement and love. Our responsibility is to do what we can, learn what we can, improve the solutions, and pass them on.
Richard Feynman vi TABLE OF CONTENTS
Page
LIST OF FIGURES…………………………………………………………………………...…vii LIST OF TABLES………………………………………………………………...……………...xi LIST OF APPENDICES…….……………………………………………………..…………....xii LIST OF ABBREVIATIONS …………….……………………………………………………xiii
CHAPTER ONE: PERSPECTIVES OF SOLID-STATE PHYSICS, INORGANIC CHEMISTRY, AND THE MATERIALS SCIENCES ...... 1 1.1. Epistemological Framework ...... 1
1.2. Modern Frameworks for Materials Synthesis ...... 6
1.3. Metal-Organic Frameworks ...... 18
1.4. Lanthanide-Metal-Organic Frameworks ...... 40
CHAPTER TWO: THE SYNTHESIS AND PHOTOLUMINESCENCE PROPERTIES OF [CE(NO3)(NDC)•2DMA]n...... 45
2.1. Synthesis of [Ce(NO3)(NDC)•2DMA]n ...... 45
2.2. Structural Characterization of [Ce(NO3)(NDC)•2DMA]n ...... 46
2.3. Stability of [Ce(NO3)(NDC)•2DMA]n ...... 53
2.4. Photoluminescence Properties of [Ce(NO3)(NDC)]n...... 55
CHAPTER THREE: THE SYNTHESIS AND PHOTOLUMINESCENCE PROPERTIES OF [ND(NO3)(NDC)•2DMA]n ...... 61
3.1. Structural Characterization of [Nd(NO3)(NDC)•2DMA]n ...... 61
3.2. Stability of [Nd(NO3)(NDC)•2DMA]n ...... 66
3.3. Photoluminescence Properties of [Nd(NO3)(NDC)]n ...... 68 vi CHAPTER FOUR: THE SYNTHESIS AND PHOTOLUMINESCENCE PROPERTIES OF [EU(NO3)(NDC)•2DMA]n ...... 76
4.1. Photoluminescence Properties of [Eu(NO3)(NDC)]n...... 80
4.2. Analysis of Aqueous Chromic Acid with [Eu(NO3)(NDC)]n ...... 82
CHAPTER FIVE: EXPLORATORY SYNTHESIS OF LANTHANIDE-METALLOID COMPLEXES FOR PHOTOCATALYSIS ...... 86
5.1. Synthesis and Characteristics of GeS-Intercalated La(OH)3 ...... 89
5.2. Identification of GeS-Intercalated La(OH)3...... 90
5.3. Band Gap Measurements ...... 96
5.4. Photocatalytic Activity of La(OH)3[GeS]0.1 ...... 99
CHAPTER SIX: FUTURE WORKS AND CONCLUDING REMARKS ...... 102
REFERENCES…………………………………………………………………………………106
APPENDICES………………………………………………………………………………….130 LIST OF FIGURES
Figure 1: Patents registered for graphene ...... 3
Figure 2: Effect of stacking in trilayer graphene...... 5
Figure 3: SHS of mixed TiB2/TiC@NiAl ...... 12
Figure 4: Isoreticular synthesis using Zn2+ centers with branched phenol ligands ...... 20
Figure 5: Interpenetrated units of MOF [Cd(BPY)(BDC)]n ...... 22
Figure 6: Effect of interpenetration on structural features ...... 24
Figure 7: Solvent effect on MOF interpenetration ...... 25
Figure 8: General mechanisms of zeolite formation ...... 26
Figure 9: Time-resolved EDXRD on solvothermal MOF formation ...... 28
Figure 10: Computational screening of MOF structures ...... 30
Figure 11: DOE hydrogen storage goals ...... 33
Figure 12: MOF patents filed and H2 Isotherms for MOFs and Zeo13X ...... 37
Figure 13: Varying synthetic conditions of [Ce(NO3)(NDC)•2DMA]n ...... 46
Figure 14: 50% TELP plot and unit cell of [Ce(NO3)(NDC)•2DMA]n ...... 48
Figure 15: Nearest distance between [Ce(NO3)(NDC)•DMA]n layers ...... 50 viii
Figure 16: 2D layer stacking of [Ce(NO3)(NDC)]n ...... 51
Figure 17: Experimental vs simulated diffraction of [Ce(NO3)(NDC)•2DMA]n ...... 51
Figure 18: As-synthesized vs. vacuum-dried [Ce(NO3)(NDC)]n ...... 52
Figure 19: FTIR spectra of [Ce(NO3)(NDC)]n and H2NDC ...... 53
Figure 20: PXRD thermal stability of [Ce(NO3)(NDC)•2DMA]n ...... 54
Figure 21: pH stability of [Ce(NO3)(NDC)]n ...... 55
Figure 22: Total luminescence spectra of [Ce(NO3)(NDC)]n ...... 56
Figure 23: Excitation and emission spectra of [Ce(NO3)(NDC)]n ...... 57
Figure 24: [Ce(NO3)(NDC)]n fluorescent emissions similar to Ce(NO3)3•6H2O ...... 58
Figure 25: Hirshfield charges on [Ce(NO3)(NDC)]n ...... 59
Figure 26: DOS of [Ce(NO3)(NDC)]n and nitrate precursor ...... 60
Figure 27: Geometric comparison of [Ce(NO3)(NDC)]n to Ce(NO3)3•4H2O ...... 60
Figure 28: 50% TELP plot of [Nd(NO3)(NDC)•2DMA]n ...... 62
Figure 29: [Nd(NO3)(NDC)]n layers viewed along the a-axis ...... 64
Figure 30: FTIR spectra of [Nd(NO3)(NDC)]n and H2NDC ...... 65
Figure 31: Diffraction patterns of [Nd(NO3(NDC)•2DMA]n ...... 66 ix
Figure 32: Thermal stability of [Nd(NO3)(NDC)•2DMA]n ...... 67
Figure 33: Total luminescence spectra of [Nd(NO3)(NDC)]n ...... 68
Figure 34: Solid-state emission of [Nd(NO3)(NDC)]n ...... 69
Figure 35: Photoluminescence of [Nd(NO3)(NDC)]n in DMF ...... 70
Figure 36: Aromatic fluorescent quenching of [Nd(NO3)(NDC)]n in DMF ...... 71
Figure 37: Quenching efficiency of analytes in [Nd(NO3)(NDC)]n ...... 72
Figure 38: Photoluminescence of benzene and [Nd(NO3)(NDC)]n ...... 74
Figure 39: Photoluminescence of organic analytes and [Nd(NO3)(NDC)]n ...... 75
Figure 40: 50% TELP plot of [Eu(NO3)(NDC)•2DMA]n ...... 77
Figure 41: 2D layer stacking of [Eu(NO3)(NDC)]n ...... 78
Figure 42: PXRD of [Eu(NO3)(NDC)•2DMA]n ...... 80
Figure 43: Total luminescence spectra of [Eu(NO3)(NDC)]n ...... 81
Figure 44: Photoluminescence of [Eu(NO3)(NDC)]n ...... 82
Figure 45: H2CrO4(aq) fluorescence quenching of [Eu(NO3)(NDC)]n ...... 83
Figure 46: Fluorescence effect of [H2CrO4 (aq)] concentration in [Eu(NO3)(NDC)]n . 84
2+ Figure 47: Ni (aq) fluorescence quenching of [Eu(NO3)(NDC)]n ...... 85 x
2+ Figure 48: Fluorescence effect of [Ni ] concentration on [Eu(NO3)(NDC)]n ...... 85
Figure 49: Illustration of the catalytic photodegradation mechanism ...... 87
Figure 50: Solar irradiance AM 1.5 reference ...... 88
Figure 51: PXRD La(OH)3[GeS]0.1 ...... 91
Figure 52: SEM micrographs and select spectra of La(OH)3[GeS]0.1 ...... 92
Figure 53: Elemental mapping of La(OH)3[GeS]0.1 ...... 93
Figure 54: EDS spectrum of side-product melamine ...... 94
Figure 55: 50% TELP plot of melamine unit cell ...... 95
Figure 56: DRS spectrum of La(OH)3[GeS]0.1 ...... 97
Figure 57: Band gap of TiO2, anatase ...... 98
Figure 58: Band gap of La(OH)3[GeS]0.1 ...... 99
Figure 59: Photodegradation by La(OH)3[GeS]0.1 ...... 100
Figure 60: Exponential decay of methylene blue by La(OH)3[GeS]0.1 ...... 100
Figure 61: PXRD of [Sm(NO3)(NDC)•2DMA]n ...... 103
Figure 62: 50% TELP plot of [Yb(NO3)(NDC)•2DMA]n ...... 104 LIST OF TABLES
Table 1: Broad Overview of Techniques in the Synthesis of Solids ...... 7
Table 2: Thermal Stability of Similar MOFs ...... 42
Table 3: Crystallographic Refinement Details for [Ce(NO3)(NDC)•2DMA]n ...... 49
Table 4: Crystallographic Refinement Details for [Nd(NO3)(NDC)•2DMA]n ...... 63
Table 5: Crystallographic Refinement Details for [Eu(NO3)(NDC)•2DMA]n ...... 79
Table 6: EDS Analysis of La(OH)3[GeS]0.1...... 93
Table 7: Crystallographic Refinement Details for Melamine ...... 96
Table 8: Crystallographic Refinement Details for [Yb(NO3)(NDC)•2DMA]n ...... 104 LIST OF APPENDICES
APPENDIX A : TABLES OF ATOMIC COORDINATES, BOND LENGTHS, AND ANGLES…………………………………………………………..….129
APPENDIX B: COMPUTATIONAL PARAMETERS………………………………..152 LIST OF ABBREVIATIONS
ΔH enthalpy of formation
ACN acetonitrile
AFM atomic force microscope b.p. boiling point
BDC 1,4- benzenedicarboxylate
BDP-iPr benzenediphosphonate diisopropoxy
BET Brunauer-Emmett-Teller theory
BPDC biphenyl-4,4′-dicarboxylate
BPY 4,4’-bipyridine
BTB 4,4’,4’’-benzene-1,3,5-triyl-tribenzoate
BTC 1,3,5-benzenetricarboxylate
BTE 4,4′,4″-[benzene-1,3,5- triyl-tris(ethyne-2,1-diyl)]tribenzoate
BTT 1,3,5-tricyanobenzene
CAM camphorate
CCD charge-coupled device
CVD chemical vapor deposition
DEF N,N’-diethylformamide
DESY Deutsches Elektronen-Synchrotron
DFT density functional theory
DMA N,N’-dimethylacetamide
DMF N,N’-dimethylformamide
DRS diffuse reflectance spectroscopy
DSC Differential scanning calorimetry
EDS energy-dispersive X-ray spectroscopy
EDXRD energy-dispersive X-ray diffraction xiv ESI-MS electrospray ionization mass spectrometry
FTIR Fourier-transform infrared spectroscopy
HPDC tetrahydropyrene- 2,7-dicarboxylate
ICP inductively-coupled plasma, inductively-couple plasma spectroscopy
IEEE Institute of Electrical and Electronics Engineers
IUPAC International Union of Pure and Applied Chemistry
KJMA relation Kolmogorov-Johnson-Mehl-Avrami relation
LDA local-density approximation
Ln-MOF lanthanide-metal-organic framework
M molarity m.p. melting point
MBB molecular building block
MOF metal-organic framework
NDC 2,6-napthalenedicarboxylate
PDC 4,4’-phenyldicarboxylate
PTFE polytetrafluoroethylene
PXRD powder X-ray diffraction, powder X-ray diffractometer
PXRD powder X-ray diffraction
RCSR Reticular Chemistry Structural Resource
RH relative humidity
SBU secondary building unit
SEM scanning electron microscope
SHS self-propagating high-temperature synthesis
SPR surface plasmon resonance spectroscopy
SSM Solid-state metathesis
TABD 4,4’-((Z,Z)-1,4-diphenylbuta-1,3-dien-1,4-diyl)benzoic acid xv Tad adiabatic temperature of combustion
Tc superconductivity critical temperature
TCPB 4,4’,4’’,4’’’-benzene-1,2,4,5-tetrayltetrabenzoic acid
TCPE tetrakis(4-carboxyphenyl)ethylene
TELP thermal ellipsoid probability (plot)
TEM transmission electron microscope
TEOS tetraethylorthosilicate
TGA thermogravimetric analysis
TM-MOF transition metal metal-organic framework
TPDC 4,4’-terphenyldicarboxylate
U.S. DOE U.S. Department of Energy
U.S. DRIVE U.S. Driving Research and Innovation for Vehicle Efficiency and Energy
Sustainability
CHAPTER ONE: PERSPECTIVES OF SOLID-STATE PHYSICS, INORGANIC CHEMISTRY, AND
THE MATERIALS SCIENCES
1.1. Epistemological Framework
Solid-state physics and materials chemistry are parallel but interconnected fields.
Codependent, each progresses with the other, yet there has remained a regrettable lack of cohesion in modern research between the two, creating a dichotomy of not only what information is sought after, but how the information is communicated both within the STEM fields and to the general public. On the one hand, modern solid-state chemistry has largely incorporated quantum electrodynamics, obfuscating the practical nature of the work. Materials chemistry approaches the same subject with a logic akin to that of an engineer- optimize the parameters until a desired outcome is achieved. Inorganic chemistry from both perspectives is reduced to either the underlying physical phenomenon or the technological achievement, while the synthesis of the material is treated like a recipe, if treated at all!
Modern solid-state theories are slowly but surely being restructured to include dimensions of quantum electrodynamics, theories of d-block metals with hydrocarbons, incremental technological advances, and other facets of condensed matter studies. In many ways, the graphene fervor of the last decade has been both an outcome of and a fount for such a rectification. The two- dimensional sp2 carbon lattice has been studied for over seventy years. A 1947 band theory treatment of single layer graphene was ahead of its time in solving for the impressive conductivity of the material1, a fact that was discussed in reference to carbon-based 2 resistors in the Proceedings of the Physical Society in 19532 but wouldn’t find its way into the
Proceedings of the Institute of Electrical and Electronics Engineers until 2009.3 In 2004, graphene caught the attention of the world when two physicists, Andre Geim and Konstantin Novoselov, were able to mechanically exfoliate a sufficiently large sample of monolayer graphene for characterization, awarding the group the 2010 Nobel Prize in Physics.4 The study of graphene quickly expanded beyond the annals of theoretical physics and became a multi-disciplinary endeavor. Figure 1 shows the number of SciFinder search hits for patents published on graphene specifically under the technology headers of ‘Materials and Products’ and ‘Processes and
Apparatus’ between 2003 and 2016, as well as the United Kingdom Intellectual Property Office data for international patents filed regarding graphene in 2013.5,6
The SciFinder patent query reflects the increased interest in a solid-state physics phenomenon to a broad audience, and as the data compiled by the UK Intellectual Property Office shows, that audience included not only universities but major international commercial entities such as IBM and Samsung.6 The graphene gold rush hasn’t yet panned out; large-scale manufacturing of high-quality graphene remains elusive despite the overwhelming number of potential applications.7 Still, the study of graphene and the excitement of the possibilities has been enough to encourage conversations between fields that often intersect but pull from a different vernacular. A 2011 IEEE Conference introduced engineers to ab-initio calculations on the
“armchair edges” of graphene and nitrogen-doped graphene and their effects on graphene-based field-effect transistors.8 The journals Polymer, Physics of the Solid State, and Electrochimica Acta have all published papers regarding the synthesis of graphene, an uncommon feat for the synthesis of any solid to receive attention from so many disciplines.9-11 3
Figure 1: Patents registered for graphene (Top) SciFinder search hits for patents published on graphene under ‘Technology’ header and filtered by ‘Materials and Products’ or ‘Processes and Apparatus’ between 2003 and 2016. (Bottom) United Kingdom Intellectual Property Office data for worldwide 2013 patents filed regarding graphene.
4 The most important outcome from the study of graphene, however, is that in just a decade, the amount of data gathered by researchers was immense and uniformLy treated. Collaboration between physicists, chemists, materials scientists, and commercial interests led to an explosion of information and opportunity.
Much of the frustration in graphene, as well as any other solid, lies in the synthesis of the material. Traditional solution-phase methods like those common to organic chemistry take advantage of consistent electronic and diffusion properties in systems of hydrocarbons and common solvents that has produced compendiums of generalizable reactions yielding nearly limitless modifications within relatively definable limits.
Efforts to establish similar reaction delineations to those that yield organic compounds have largely failed. The analogue to organic chemistry is myopic not only because inorganic reactions call upon larger tropes of the periodic table but also because there is a larger variation in outcomes. The properties of an inorganic solid are dependent on the structure, so both allotrope, i.e. variations in the molecular crystal structure, and morphology, i.e. macromolecular superstructure, are key factors. For instance, monolayer graphene receives a lot of attention for its unique electrical properties. As graphene layers stack, however, the properties drastically change, even though each layer is identical. For instance, tri-layer graphene most commonly stacks in configuration ABA, but is known to occasionally stack in configuration ABC, as shown in Figure
2. When a perpendicular voltage is applied across ABA graphene, not much happens. However, when that same voltage is applied to ABC graphene the band gap changes proportionally with the bias.12 5
Figure 2: Effect of stacking in trilayer graphene ABA (top left) and ABC (top right) structural configurations of trilayer graphene shown with computational model of the band gap without applied bias (green) and with applied bias (red). The plot shows the change in band gap with respect to bias- induced electric displacement ABC stacked graphene.
Such tunable band gap materials are widely sought after for applications in everything from electronics to optics. If the top layer of ABA graphene could only be moved by eight-billionths of an inch! Small changes in morphology can have significant impacts in application. The challenge, then, lies in controlling both the crystallinity and the morphology, both of which have some dependency on composition. Composition is not the sole driver of molecular structure or 6 supramolecular morphology of a solid, and therefore is insufficient in predicting intrinsic properties.
The frustration caused by the limited ability to predict properties and design materials accordingly isn’t a marginal issue. Through the Stone Age to the Bronze Age, past the Space Age, and up to the Information Age sprung from Silicon Valley, technological advances rely directly upon advances in the synthesis of new solids. Nevertheless, new solids are almost exclusively synthesized through exploratory methods, using a combination of educated guesswork, intuition, and unexplained previous success as lodestars. The challenge in uncovering the new materials for the next wave of innovation will come from a thorough understanding of the dynamics of solid- state synthesis.13
1.2. Modern Frameworks for Materials Synthesis
Synthesis methods for solid-state materials can generally be categorized by temperature.
Table 1 provides a general overview of the most common techniques for the synthesis of inorganic solids. While an exhaustive treatment of the synthesis of novel solids will not be provided, some common methods will be discussed as a point of context. Seeded methods, coating methods, and surface modifications are extremely important, but are not used in the investigation of purely novel materials and will not be considered, though mixed and layered materials offer novel and/or enhanced properties.
7 Table 1: Broad Overview of Techniques in the Synthesis of Solids 8
High-temperature synthesis methods are those generally above 500 °C and include traditional direct methods14-19, flux melts20-23, self-propagating high-temperature synthesis
(SHS)24-25, and chemical-vapor deposition (CVD)26-27. Closer to ambient temperature (0 – 500 °C) routes include solid state metathesis (SSM)28-31 , sol-gel chemistry32-35, and solvothermal synthesis.36-40 Mechanical activation methods are also prominent, but here will be treated as an additive process, not a standalone synthetic route. Mechanical activation involves ‘activating’ reagents by excessive milling, which is shown manuto decrease the average particle size of the reactants and decrease the activation energy of a reaction, resulting in higher yield and improved crystallinity.41-42 By extension, pure mechanochemical reactions have received attention as a viable route for the new synthesis of known materials and a promising route for the synthesis of novel materials, both inorganic and organic.43 Materials thus synthesized are relatively uncommon, or simply less characterized, and will not be discussed. There is substantial overlap between methods; high-temperature methods often require solvated precipitation at roughly ambient conditions and the low-temperature methods often require calcination at temperatures exceeding 500 °C.
At the forefront of solid state synthesis and materials science, traditional direct methods are still often the first route by which novel materials are synthesized. In 1986, the search for superconducting materials was invigorated with the direct synthesis of barium lanthanum copper oxide, the first material to exhibit superconductivity above 30 K (Tc=35 K), a milestone of superconductivity.16 The discovery inspired a generation of novel quaternary cuprates synthesized using the ceramic method. Within a year the next major milestone in superconductivity was
18 reached with the direct synthesis of yttrium barium copper oxide. The YBa2Cu3O7-x species exhibited superconductivity above the boiling point of liquid nitrogen (77.4K) for the first 9 time.17-18 As of this publication, the highest critical temperature reported for any material under ambient pressure is quinary cuprate superconductor HgBa2Ca2Cu3O8, Tc= 133 K, originally synthesized via a ceramic method first reported in 1993.19
Superconductors are not a cherry-picked topic to show how relevant ceramic-synthesized solids are at the forefront of materials science. A more recent example can be seen in Dirac semimetals, billed as a three-dimensional graphene due to their similar conductance properties but
14 in more than just a single plane. In 2014, the first significant Dirac semimetal, Na3Bi, was successfully synthesized via ceramic methods for characterization.14
Direct synthesis is not a viable option for many materials. Of current interest, the synthesis of nanomaterials is virtually unheard of via direct high-temperature synthesis; nanoparticles are widely reported to aggregate into bulk metal at temperatures exceeding 300 °C, and organic binders and surfactants that stabilize nanoparticles break down just above those temperatures.44
Further, direct synthesis can be assumed to favor the thermodynamic product, precluding the formation of the kinetically feasible product, and because synthesis is directly limited by mass transport, lack of substantial single-crystals or low yields can prevent adequate testing.45 Direct, high-temperature synthesis is not always a viable route to bulk thermodynamic product, either.
There are instances in which the diffusion of reactants into intermediates has an unattainable activation barrier, or that the energy to achieve potential reactant intermediates is simply inaccessible by temperature or pressure.46 This is particularly true for multinary compounds, i.e. compounds of three or more elements.
Flux melts are often necessary for ternary systems and higher. Single-crystals of ternary refractory ceramics have been synthesized directly for at least 50 years.47 Still, the search for 10 intrinsically hard materials has largely moved beyond direct synthesis.48 The synthesis of tantalum aluminum carbide phase Ta3Al2C was first reported via arc furnace in low yields in 1963, with no references reporting a successful direct synthesis.49 However, high yields of single-crystalline tantalum aluminum carbides Ta3AlC2 and Ta4AlC3 using aluminum as a reactive flux at 1500 °C have been achieved.50 Single-crystal synthesis with optimal yields of a variety of ternary and quaternary carbides, silicides, and nitrides have all been reported using molten metal fluxes, though most of the compounds have also been synthesized directly.45 The use of a flux improves diffusion during a reaction, though, affording lower temperatures and shorter durations, often with improved crystallinity.45 A study comparing direct synthesis of praseodymium-doped cerium oxide to flux synthesis in eutectic KOH/NaOH salt flux dropped the synthesis temperature from
1300 °C to 600 °C and the heating time from 120 min to 30 min.51 Still, often direct methods may require days, while flux methods require tens of hrs.45
Both ceramic and flux syntheses are energy and time intensive. Even when pressure is not a consideration, controlling oxidation, thus controlling atmosphere, is necessary at high- temperatures. Further, reaction times vary from hours to days, and in at least one published case,
4.6 months.52 Self-propagating high-temperature synthesis (SHS) can take advantage of chemical energy to decrease temperature input and reaction time. SHS makes use of adiabatic combustion energy released from an ignition point of an exothermic reaction to yield product, essentially replacing the furnace with chemical energy.53 This imposes the criteria that some part of the reaction has a sufficient adiabatic temperature of combustion, Tad , leading to a sufficiently exothermic enthalpy of formation ΔH of the product.53 On one hand, this limits the reactions that can be done; on the other it allows for potential syntheses to be screened using compendiums of 11 physicochemical quantities as well as study system thermodynamics and mechanics. For instance, the propagation of the exothermic wave front produced by a reaction, the combustion velocity, and the combustion temperature allow reaction rate and activation energy of product formation to be determined.53
Measuring the combustion from the ignition of copper and selenium powder in a vacuum, the exothermic wave front was measured to travel an average velocity of 5.6 mm/s, leaving behind phase-pure copper (II) selenide, a very fast synthesis compared to direct and flux methods.25 The combustion front velocity for the formation of intercalated TiB2/TiC and TiB2/TiN sintered on to
NiAl by SHS (3Ti + B4C 2TiB2 + TiC, Tad = 2510 ΔH = -753.2 kJ and 3Ti + 2BN 2TiB2 +
2TiC, Tad = 3050 ΔH = -753.2 kJ) was measured to vary between 1.4 mm/s and 5.7 mm/s, depending on the ratio of Ni/Al.54 Figure 3 shows the propagating wavefront, as well as data on the reaction kinetics; from the wavefront kinetics, the activation energy of the system was found to be 102.5 kJ/mol for the TiC system and 133.4 kJ/mol for the TiN system.54 Ternary systems have also been reported, though as with flux synthesis the compositional ratios differ from the results of direct synthesis, making it possible SHS can yield kinetically formed product vs thermodynamically stable product.55 Solids resulting from SHS are often homogenous, and single- crystal growth is uncommon but not unheard of.56 With ceramic, flux and SHS methods, morphological control is virtually impossible. Another complicating 12
a)
b)
c)
Figure 3: SHS of mixed TiB2/TiC@NiAl
a) SHS reaction x(Ni + Al) + 3Ti + B4C xNiAl + 2TiB2 + TiC showing propagation front after ignition with reaction time below each image. b) SHS reaction y(Ni + Al) + 3Ti + 2BN yNiAl + 2TiB2 + 2TiN showing propagation front after ignition with reaction time below each image. c) Arrhenius plot from measured wave front velocities and combustion temperatures establishing the activation energy of each reaction.
13 factor is separations. If some reactant fails to react, or multiple products form, both of which happen often, separations can be difficult or impossible. Chemical vapor deposition addresses some of these issues.
Chemical vapor deposition (CVD) is the process by which gasses and/or vapors react at or near a substrate surface and deposit as a solid. CVD has been shown to offer more morphology control than other high-temperature synthesis methods. This is in large part because the rate at which reactants are introduced to a substrate can be controlled. In a study of molybdenum disulfide deposition on silicon nanowire arrays, Chen et al. showed that controlling the rate of sulfur evaporation predominantly controlled the nucleation rate of deposited MoS2, thus in turn the average particle size, and the screw dislocation axis in the superstructure morphology, impacting the final surface area.27
Morphology and composition of the CVD substrate are also significant contributors to the final product. Studies on the deposition of graphene have shown that grain boundaries in a substrate correlate to grain boundaries in the deposited graphene.57 Even more telling, Shin et al. compared graphene deposition on three single crystal copper faces with Miller indices (111), (200), and
(220), and found that the face with the most similar interfacial lattice to graphene, (111), had a deposition rate about twice that of other orientations.58 Using the morphology of a substrate as a template, CVD can be very effective in controlling the morphology of the product. Shimizu et al. were able to use a known etching process to produce highly-regular honeycomb pores in aluminum oxide to create a template on which to deposit silane, resulting in highly regular Si111 nanowires.59
A primary downside to CVD is the difficulty and expense in producing large amounts of product, which is a significant barrier for the commercial manufacturing of pristine graphene.7 14
Low-temperature synthetic routes can achieve high yields more easily than high- temperature methods by taking advantage of traditional benchtop solution chemistry. Diffusion of reactants in high-temperature synthesis methods, particularly ceramic and flux methods, is limited by mass transport. The most practical way to overcome this problem is by dissolution, since a solution can practically be modeled as a homogenous mixture of reactants within a solvation sphere. Solid-state metathesis (SSM), sol-gel and solvothermal methods use soluble or homogenously colloidal metal/metalloid precursors to precipitate solids.
SSM represents a broad class of reactions that straddle low-temperature and high- temperature solid synthesis, depending on whether a benchtop solvent or a molten compound is used. An extension of the solubility and precipitation rules presented in first-semester general chemistry, the driving force behind SSM has historically been to replace high-temperature methods with faster, low-energy alternatives by using soluble precursors.60 Crystals of many metal nitrides, arsenides, and phosphines can be synthesized readily in high yields by simple reactions between metal-halides and trisodium salts at temperatures under 500 °C in less than one hour.60 SSM has been extended to include the impregnation of porous structures with nano- to micro- scale compounds, making it a useful route for intercalated or doped catalysts, which may be deactivated by changes in oxidation or structure that can occur during high-temperature synthetic routes.
Looking at a well-studied cathode catalyst for solid-oxide fuel cells, Ni@Y2O3-ZrO2 synthesized via SSM resulted in significantly less agglomeration and sintering of the Ni catalyst than the direct- synthesized compound, achieving improved performance of the electrode.29 These methods are able to produce homogenous microcrystalline materials but reports of substantial single-crystal growth are rare for anything beyond binary systems.28, 31 Regardless, SSM may be able to produce 15 the kinetic product of a reaction, while high-temperature methods overwhelmingly yield the thermodynamic product. A kinetic trapping mechanism, supported by differential scanning calorimetry and powder X-ray diffractions, of metathesis of iron (II) chloride and sodium disulfide
61 in molten sulfur have been shown to produce phase pure iron (IV) sulfide, FeS2, at 350 °C. Such kinetic trapping enables SSM to produce variants difficult to access with high-temperature methods.
Sol-gel synthesis sprang forth from silicon-alkoxy gel chemistry as far back as the 19th century and has broadened into a method for producing varieties of metal oxides, particularly nanoscale morphologies.62-63 A comprehensive 2016 review of sol-gel synthesis parameters and procedures details the current working model for the synthetic route: the sol-gel process starts with the preparation of a colloidal suspension of inorganic salts or alkoxides, which undergoes hydrolysis in the presence of water and/or an alcohol, forming a gel-like metal-oxo-metal or metal- hydroxy-metal polymer with alkoxy-branches, which then ‘ages’ over time until the solvent has dissipated forming a ‘xerogel’ at which point final solid product is obtained by calcination and/or washing.34
Each step of the sol-gel process has a variety of key parameters influencing the resultant solid, complicating the ability to generalize sol-gel reactions. In studies on tetraethylorthosilicate
(TEOS), a sol-gel precursor for silicon dioxide and one of the first sol gel systems studied, pH of the initial solution affected the rate of hydrolysis: at a low pH hydrolysis occurs more quickly than at a high pH, resulting in different morphologies.64 More recent studies on ZnO formed via sol gel found from pH 8-11, particle size is inversely proportional to pH due to a competing reaction,
- 2- Zn(O) +H2O + 2OH Zn(OH)4 ,decreasing the aggregation rate of the particles during 16 aging.35Other factors that control the rate of hydrolysis are temperature and alkoxy group, both of which can have an effect on the final morphology of the material.64
Slowing the gelling process that occurs after hydrolysis and condensation also has a significant impact on the structure of the solid product. Ward and Ko showed that for zirconium oxide formation, there is a desirable length of time the synthesis should be in the gel stage related to pH.65 Too little acid and precipitation occurs quickly, preventing the branching that occurs during gelling, leading to low surface areas; too much acid and too much branching occurs, leading to a collapse of pores during calcination leading to low surface areas.65 With just the right amount of acid, however, the alkyl group will be protonated just enough to allow just enough branching to occur prior to precipitation that the precipitated material will be able to maintain its pores during calcination, leading to a maximum in surface area.65 Through various stages of the reaction, the sol gel method offers some control over morphology, particularly pore size and surface area, and in general produces micro- and nano-scale morphologies, potentially preventing structure determination in novel materials using single-crystal X-ray diffraction.
Among the low-temperature methods, solvothermal synthesis likely produces the largest crystals. Attractive in part because synthesis is usually ‘one-pot’, dissolved reagents are heated in sealed, PTFE acid digestion vessels to prevent solvent evaporation and build relatively small but consequential pressure, or reagents are heated under reflux conditions. Solvothermal methods include hydrothermal methods, and can produce a wide array of materials, from nanostructured
66 photoelectric chalcogenides such as Bi2S3, to single-crystals of quaternary sulfides like
36 Na4Cu32Sn12S48, and metal-organic frameworks (MOFs) such as the record internal-surface-area- 17 material [Cu3(tris(5-([4-phenylethynyl)phenyl]ethynyl]benzene-1,3-dicarboxylate)
†,67 benzene)(H2O)3]n.
Solvothermal synthesis was born out of hydrothermal synthesis techniques known to produce high-quality crystalline samples of industrial significance, such as catalytic zeolite ZSM-
5 and synthetic quartz used in piezoelectrics.68-69 Beyond crystal quality, more than any other synthesis method for solids, solvothermal recipes are often fungible for isostructural materials of similar composition. This phenomenon was reported as early as 1963 when Christensen and
Rasmussen reported a single hydrothermal synthesis method for perovskite structure barium
70 titanate, BaTiO3 and variants CaTiO3, SrTiO3, CdTiO3, PbTiO3, and BaZrO3. A 1993 study used microwave-assisted hydrothermal synthesis to produce perovskite-structured barium titanate,
BaTiO3 and isostructural variants SrTiO3, Ba0.5Sr0.5O3, PbTiO3, BaZrO3, SrZrO3, and even
71 Pb(Zr0.52Ti0.48)O3 under similar conditions. SEM micrographs from the study show morphology varied by compound from spheres to plates to orthorhombices and from submicron particles to particles larger than 10 μm (3 orders of magnitude), indicating the parameters used may have produced isostructural compounds, but can’t be extended to analogous morphologies.71
The effect of solvent is likely a significant factor on the control of morphology and particle size in solvothermal synthesis. Competing reaction mechanisms have been posited for the hydrothermal synthesis of barium titanate.72-73 One study found evidence for at least two competing mechanisms: a homogenous nucleation point in which small amounts of dissolved titanium dioxide react directly with dissolved barium oxide to form barium titanate, and a heterogenous nucleation point in which barium cations and hydroxide anions diffused into an undissolved titanium dioxide lattice and water diffused out, forming barium titanate .72 18
Preventing multiple mechanisms is necessary to curb the formation of multiple morphologies. Uniform, spherical nanocrystals of 6nm diameter perovskite barium titanate were produced using alkoxy precursors and phenylmethanol as the solvent, which may preclude multiple mechamisms.74,75
Solvothermal methods have been shown to be generalizable for perovskite-based structures, and this has also been true for porous materials such as zeolites and metal-organic frameworks.76-77 Solvothermal synthesis has produced the largest library of so called ‘rational’ methods, as opposed to most approaches in solid synthesis, which are trial-and-error based. This has been especially important for a hybrid inorganic-organic class of materials known as metal- organic frameworks (MOFs).
1.3. Metal-Organic Frameworks
Early analogs of MOFs were a class of crystalline solids called coordination polymers that resulted from sol-gel reactions of organic compounds and metal-salts.78 Modern MOFs, though, are more similar to zeolites; the earliest metal-organic frameworks were synthesized hydrothermally and posited as analogues both in structure and function.40An early review by
Christoph Janiak painted MOFs as more versatile than zeolites and concludes,
Coordination polymers, which can also be seen as a meeting ground for the subdisciplines of molecular and solid-state inorganic chemistry, bring together synthetic techniques … for designing and investigating extended structures with specific physical properties by low-temperature reactions. 79
Written in 1997, Janiak touched base on an important aspect of metal-organic framework synthesis that researchers in the field were developing. MOFs offer the potential to design application by 19 designing the appropriate ligand, and solvothermal methods allow for such flexible synthetic demands.
By 2003, a review for Nature by Omar Yaghi, a prominent MOF investigator, opens with a common grievance, “… the discovery of new compounds has been mostly serendipitous, using methods …‘shake and bake’, ‘mix and wait’ and ‘heat and beat’” but concludes his review with,
“…design of the structural skeleton coupled with the ability to control its chemical functionalization and adjustment of its metric dimensions present exciting prospects.”80 Yaghi is referring to the reticular aspects of MOF synthesis. If a motif of a metal-center with a given coordination and ligand(s) with certain structure and composition are known to crystallize under given conditions, then using structurally analogous ligands and metal centers that coordinate the same way will also crystallize in the same conditions. Such motifs are commonly referred to as secondary building units (SBU’s) or molecular building blocks (MBB’s). Reticular solvothermal synthesis allows for precision in the otherwise capricious world of inorganic synthesis. Figure 4 shows a prominent example of reticular synthesis producing five metal organic frameworks.81
As Figure 4 illustrates, Furukawa et al. were able to design four analogous MOFs based on previously synthesized and characterized MOF-205, a structure with octahedral Zn4O(CO2)6. 20
Figure 4: Isoreticular synthesis using Zn2+ centers with branched phenol ligands
21 centers connected by ligands BTB and NDC oriented perpendicularly.81 Pore size and internal surface area were made larger by design by substituting analogous but larger ligands under homologous conditions.81 The most notable new structure rationally designed by this study substituted BTB with BTE, an analogous molecule but with binding sites stretched further by a triple-bonded carbon, and BPDC instead of NDC, also analogous but increased in size by the length of a carbon-carbon chain.81 The resulting MOF-210 exhibited a BET surface area of
2 81 6240m /g, in 2010 the highest of any published crystalline material. MOF-210 did not hold the record for BET surface area for long; later in 2010, Farha et al. at Northwestern University published structure NU-110, and by successfully stretching BTB even further by adding a phenyl and an ethyne group into the already large, branched ligand, created a framework with the as-yet unsurpassed BET surface area of 7140m2/g.67
Not only does the study show the molecular structure of the ligand can be tailored to optimize surface area, Farha et al. were further able to control topological elements of the unit cell.
By using bidentate ligands, and assuming the conditions would lead to tetrahedron binding around the metal center as it had in the isoreticular synthesis series of Furukawa et al., Farha et al. were able to design a ‘paddlewheel’ topology, known in reticular chemistry terms generated by the
Reticular Chemistry Structure Resource (RCSR) atlas as an rht-topology.67, 82 An important feature of the rht-topology is that it precludes unit cell interpenetration, a topological feature brought about when otherwise independent axes of a unit cell are overlapping, ultimately decreasing internal surface area.82
Interpenetration is a common structural phenomenon. Figure 5 compares a non- interpenetrated MOF to its interpenetrated variant.83 22
Figure 5: Interpenetrated units of MOF [Cd(BPY)(BDC)]n (labelling from ref. 82) a) The non-interpenetrated unit of [Cd(BPY)(BDC)]n. b) The non-interpentetrated unit viewed along c-axis. c) Wireframe representation of non-interpenetrated unit. d) The interpenetrated unit of [Cd(BPY)(BDC)]n e) The interpenetrated unit viewed along b-axis. f) The wireframe representation of interpenetrated unit cells.
For a pair of orthorhombic MOFs derived from octahedral Cd2N4O8 blocks bridged by BPY and BDC, interpenetration was shown to be a function of both temperature and concentration.
Briefly, at low-temperatures (85- 95 °C) and low concentrations (0.0125 M) only non- interpenetrated product forms.83 At temperatures 115- 125 °C and 0.05- 0.10 M only the 23 interpenetrated product forms.83 Intermediate temperatures and concentrations result in the formation of both phases.83
Studies on the synthesis of MOFs containing Zn4O(CO2)6 centers linked by aromatic ligands BPDC, HPDC, PDC, and TPDC have also indicated dilute conditions lead to the non- interpenetrated phase, leading to increased surface areas and larger pore-apertures.84 The interpenetrated products have approximately twice the density of the non-interpenetrated products, and pore-apertures are larger for the non-interpenetrated variants, shown in Figure 6.84
While non-interpenetrated structures are frequently sought after because of the larger pore apertures and increased internal surface areas, it is significant that synthetic parameters can be used to predict and control this element of structure. The effect of temperature and concentration on interpenetration suggests that solubility has a significant impact on the nucleation events that leads to crystal growth. At least one study has demonstrated that solvent steric effects also play a role. A series of chiral MOFs using metal-salen complexes as ligands synthesized in N,N’-dimethylformamide, N,N’-diethylformamide, and N,N’-dibutylformamide, resulted in somewhat tunable interpenetration, in which bulkier solvent resulted in non- interpenetrated phases only (Fig 7). 85 24
Figure 6: Effect of interpenetration on structural features 25
Figure 7: Solvent effect on MOF interpenetration
As with the perovskites discussed earlier, the formation of MOFs can proceed through several steps dependent not only on the solvent and reaction conditions but the precursors.
Understanding the mechanism by which MOFs form can not only help predict successful synthesis, but also guide structure. Due to their more extended history and industrial importance, zeolite formation has been studied much longer than MOF formation. Nucleation and growth of zeolites can broadly be categorized by the three following mechanisms: monomer-type crystallization in which crystals nucleate from polymerizing oligomers, the SBU model in which nucleation occurs from the assembly of solvated preformed framework monomers, and nanoslab formation, in which colloidal nanoparticles aggregate to form crystals. Figure 8 provides a graphical representation of each model.86 26
Figure 8: General mechanisms of zeolite formation
Many studies have suggested the SBU model dominates MOF formation. In an in-situ ESI-
MS (electrospray ionization-mass spectrometry) study on MOF [Mg2(Hcam)3•3H2O•NO3•ACN]n ,
+ 87 mass spectra identified SBU Mg2(Hcam)3 as the primary species in solution. Epitaxial growth of HKUST-1 [(Cu3(BTC)2•3H2O )]n monitored by surface plasmon resonance spectroscopy (SPR) showed that growth occurred more quickly when metal precursors with solvated geometries most similar to that of the framework geometry were used; i.e. the rate of growth of HKUST-1 in water is increased using copper (II) acetate vs copper (II) nitrate. 88 Further, the study showed growth rates for the (100) face was faster than that of the (111) face, indicating anisotropic growth primarily controlled by the orientation of the functional groups of the ligand.88 27
A few studies have used energy-dispersive X-ray diffraction (EDXRD) to monitor in-situ structure formation, a powerful tool that allows for quantitative determinations of crystal growth rate and activation energy.89-91 Time-resolved reflections of HKUST-1 growth were collected at temperatures from 85 to 125 °C; the pattern for growth at 125 °C is shown in Figure 9a.89 Peak positions and intensities show nucleation and growth are consistent with a steady-state transient period throughout the measurement, in agreement with an SBU formation model, and the activation energy was found to be 73.3 kJ/mol (Fig. 9c), which is comparable to hydrothermal activation energy found in zeolite Si-TPA-MFI growth, measured by time-resolved USAXS to be
83 kJ/mol.89, 92 The data used to determine the kinetics are shown in Figure 9b.89 A similar study found the activation energy for growth of MOF CAU-1-NH2 to be 136 kJ/mol for both conventional oven and microwave-assisted synthesis, with reflection patterns for each consistent with SBU-model growth.90
a) b)
28
c) d)
Figure 9: Time-resolved EDXRD on solvothermal MOF formation a) Time-resolved EDXRD pattern for HKUST-1 formation at 125 °C. b) The growth rate constant for each temperature was found from the fit between crystallization and the integrated intensity of the (222) reflection using the KJMA relation. c) From the growth rate data and temperature, the Arrhenius relation was used to determine the activation energy to be 73.3 kJ/mol. d) MIL-53(Fe) formation starts with a different phase under the conditions studied.
Microwave synthesis, though, occurred at a higher rate and resulted in smaller crystals, indicated an increase in nucleation sites.90
Studies on the formation of terephthalate MOF MIL-53(Fe) at 150 °C, however, show growth starts with an induction period of MOF-235, an iron- terephthalate MOF in the hexagonal
P6̅2c (Hall notation93), which ripens to form MIL-53, in the orthorhombic Imma.89 Moreover, the geometries of the SBUs of each framework are dissimilar, indicating the formation of MIL-53(Fe) involves a solid-state transformation.89 The EDXRD reflections at 150 °C (Fig 9d) show the formation of the (011) face of MOF-235 before the phase change into MIL-53.89
Given the complexity and variety of the structures reported, it is surprising that studies to date have such neat agreement with the SBU-growth model. Mechanistic determinations on MOF systems are still in their nascency, though, and there is at least some proposition of a nucleation 29 building unit model, as opposed to a secondary building unit model, in which nucleation sites that may or may not be identical to framework geometry sites, direct structure.94
Current work in the prediction of both structure and application is promising. Grand- canonical Monte Carlo simulations on electrostatic interactions modeled using DFT calculations on known structures and carbon dioxide were shown to accurately predict CO2 uptake from 0.1 to
1.0 bar.95 Using the SBUs derived from crystal structures, one group generated a library of 102 building blocks of metal vertices and organic linkers, and applied a structural fitting algorithm that generated over one hundred thousand possible structures, both known and novel.96
A similar Monte Carlo screening process was then used to sort by methane uptake, and identified a new structure NOTT-07 as the best candidate, theoretically higher than previously identified MOF PCN-14(Fig. 10, top).96 NOTT-07 was synthesized and methane uptake tested.
NOTT-07 did not exceed the methane adsorption capability of PCN-14 (Fig. 10, bottom), but it came impressively close.96 Designing synthesis to lead to desired compositions and structures is indeed the promise MOFs offer. However, its full potential will not be realized until there is a better understanding of the mechanisms that guide MOF formation, finally allowing for stable structures to be predicted, synthesized, and applied.
30
Figure 10: Computational screening of MOF structures Referring to Figure 10, predicted isothermal adsorption of methane from Monte Carlo simulations on hypothetical MOFs constructed from a library of SBUs derived from crystallographic information on MOFs a) Methane adsorption as a function of volumetric surface area; red dots indicate non-interpenetrated variants b) methane adsorption as a function of gravimetric surface area c) Methane adsorption showing optimized void fraction around 0.8 d) 31
3 -1 Frequency of functional group for methane adsorption greater than 205 cm STP vol e) Frequency
3 -1 of functional group for methane adsorption greater than 325 cm STP vol f) Methane adsorption by pore aperture; inset shows subset of data analyzed g) ligand identified by simulation to be optimal for methane adsorption h) ligand in PCN-14, structure previously found to have optimal methane adsorption i) Simulated and experimental data for both NOTT-107, the structure identified to be optimized, and PCN-14, the structure previously reported to have optimal methane adsorption.
The early excitement around MOFs as a new material was in the field of gas storage. While methane storage is not inconsequential, a more attractive application is the adsorption of hydrogen gas. With many recent advancements in hydrogen fuel cell technology, hydrogen gas has the potential to be a viable alternative to fossil fuels, particularly for consumer vehicles. Compressed hydrogen tanks not only present safety hazards, but repulsive forces cause the work necessary to compress hydrogen to be significantly higher than the isothermal Maxwell relationship predicts, leading to inefficiency.97 Investigating porous adsorbents is likely to lead to a safe, practical, and efficient way to store the gas as a fuel.
The U.S. DRIVE partnership with the U.S. DOE has set the 2020 goal for onboard hydrogen storage to be 45.0 g H2/ kg (gravimetric) or 30.0 g H2/L (volumetric) between -40 and
60 °C under 100 atm pressure.98 Current progress in hydrogen storage for a variety of compounds is shown in Figure 11.99 The only class of materials that that currently meet the energy goals are the so-called ‘chemical hydrogen’ sources, which are organic and organic-like compounds with covalently bonded hydrogens that produce hydrogen gas upon decomposition or oxidation.100 The process necessitates that the chemical hydrogen source either be economically regenerated or mass 32 produced, and that the byproducts are not hazardous. As yet no viable chemical hydrogen process has been identified.100
Early results for room temperature hydrogen uptake were promising. In 2003, IRMOF-6, zinc tetrahedra bridged by 1,2-dihydrocyclobutabenzene-3,6-dicarboxylic acid, showed a room- temperature gravimetric uptake of 1.0% at 20 bar.101 Designing a framework with exposed metal sites in the pores, a Mn-BTT MOF was synthesized that exhibited reversible hydrogen uptake of
12.1 g/L at room temperature and 90 bar in 2006. 102 Since then there has been no progress near room temperature for pure MOFs. Cryogenic conditions have had significant strides, though, reaching 99.5 g/kg at 77 K.103 Strategies to improve adsorption at room temperature are focused on using computational methods to identify optimized structures, as well as hybridizing with other adsorbent materials, such as graphene oxide composites.104-105
The complex structures of MOFs permit many more applications than gas storage.
Luminescent properties can be tailored into MOFs through the metal, ligand, or both. Fluorophore- based ligand TABD was synthesized with Mg2+, Ni2+, and Co2+ metals to make three MOFs exhibiting fluorescent quantum yields at 411 nm of 38.5%, 1.12%, and 0.15% , respectively, in a
106 ligand to metal charge transfer process. Incorporating the fluorescent 4-cyanobenzoate (λEx=354 nm, λEm=427 nm) as a ligand, silver MOF [Ag(cyanobenzoate) •H2O]n was found to have an increased fluorescent intensity at 427 nm, as well as additional metal-to-ligand emissions at 513,
566, and 617 nm, effectively acting as a white phosphor.107 33
Figure 11: DOE hydrogen storage goals Hydrogen goals set by the DOE, compiled by the Fuel Cell Technology Office and the Office of Energy Efficiency and Renewable Energy.
Metal-to-ligand, ligand-to-metal, ligand-to-ligand, and metal-to-metal charge transfers resulting in photoluminescence have all been reported for MOFs.108
Taking advantage of these photoluminescence properties, MOFs can be used as chemical sensors. UiO-61@N, a zirconium and 2-phenylpyridine-5,4-dicarboxylic acid based MOF, has been shown to be selective for trinitrophenol in water as a fluorescent-quenching nitro-based explosives detector, hypothesizing that when excited, free basic sites on the pyridyl ligand are able to have highly-efficient electronic interactions with trinitrophenol selecting out even trinitrotoluene.109 Selectivity is an issue for all chemical sensors. Many MOFs have been shown 34 to fluoresce even at high temperatures, a rare trait for polymers or molecular crystals. MOF
[Zn2(TCPE)]n was shown to have a highly-selective fluorescence shift caused by ammonia gas at
100 °C, but was not selective at lower temperatures.110 The complex nature of the structures, along with the inherent electronic properties arising from metal-ligand-analyte interactions leads to a
2+ huge variety of chemical signaling possibilities. By incorporating luminescent Ru(bpy)3 into the framework of bioMOF-1, aqueous Hg2+ ions were detected at concentrations as low as 0.53 pM from a selective Hg2+ -induced chain-effect breakdown of the framework releasing fluorescent
2+ Ru(bpy)3 into solution, detected using either fluorescence (LOD = 8.2 pM) or electrochemiluminescence (LOD = 0.53 pM).111 The complex structures and electronic systems of the frameworks often lead to unexpected but noteworthy synergies.
The high internal surface areas and rich diversity in chemical reactivity also make MOFs good candidates for catalysis. As shown earlier in Figure 7, metal-organic frameworks have comparable conversion efficiency and enantioselectivity to analogous homogenous catalysts.85 A
MOF designed with a chiral Ti-BINOL-type ligand was found to have conversion efficiencies over
90% and entantiomeric excesses over 80% for the conversion of aromatic aldehydes to S- secondary alcohols at room temperature, comparable to, and in some instances an improvement over, the homogenous catalyst.112-113
Important aspects of any heterogenous catalyst is recyclability and stability. In a study including recyclability, a Cu-MOF functionalized with trifluoromethylaniline for increased thermal and water stability was used as a catalyst for dihydropyrimidones and saw a 4% decrease in catalytic conversion after 4 cycles, with some degradation apparent on the powder diffraction patterns.114 35
When using a metal organic framework, stability is always a relevant question. Difficulty in reproducing high cryogenic hydrogen adsorption in [Zn4O(BDC)3]n, MOF-5 was found to be due to water degradation that occurs within minutes of exposure to ambient conditions, leading to
115 the collapse of the structure into [Zn3(OH)2(BDC)2]n, MOF-69C. The material was even found to be thermally stable in a vacuum up to 200 °C; but measured BET surface area after synthesis was 572 m2/g, then after six weeks in open air, the BET surface area was 47 m2/g.116 This problem isn’t unique to MOF-5. Vacuum-dried MOF-177, Zn4O6 units linked by branched- phenol ligand
BTB, was shown to exhibit no crystallinity after just three days in open air at 40% relative humidity.117 These are relatively extreme examples, and with so many materials falling under the
MOF umbrella, there is a wide spectrum of stabilities.
Hydrothermally-synthesized MIL-101, formally [Cr3 F(H2O)2(BDC)3• H2O]n, was found to be stable to 275 °C in open air by TGA, and showed no room temperature decomposition from water or a variety of organic solvents.118 Further, the UiO-66 family of zirconium MOFs, based on
[Zr6O4(OH)4(BDC)6]n ,was found not only to be water stable (even boiling water), but photocatalyze water splitting.119 MOF-5, MIL-101, and UiO-66 indicate some relationship to changing the metal, and so the coordination environment, led to increased stability. The trade-off is that between these MOFs, with the same ligand but different metal precursors, isoreticular conditions of using similar synthesis parameters and generating analogous, predictable structures are not met, ceding the benefit of rational design.
Further, it would be hasty to assume that the metal was strictly to blame and coordination could be weighted heavily as an indicator of stability. Almost inevitably, UiO-67, isostructural to
UiO-66 but the ligand BPDC is one phenyl group extended, was found to quickly decompose in 36 the presence of water, much like MOF-5.120 Coordination geometry and solvent accessibility of the metal center are contributing but confounding factors. ZIF-8,a cubic MOF with ZnN4 tetrahedra bridged by 2-methylimidazole, akin to MOF-5, a cubic MOF with ZnO4 groups bridged by benzenedicarboxylic acid, was shown to be thermally stable to 450 °C and submerged in boiling water, benzene, methanol, or sodium hydroxide for seven days with no measured solubility and
121-122 little change in crystal structure and N2 adsorption properties. The increased chemical stability, exhibited by several isoreticular variations of ZIF-8, has been attributed to the Zn-N-Zn bridging angle, which is near the approximate 145° Si-O-Si angle common to zeolites.122
Still, while not often confronted in literature due to a combination of optimism and work- endowment, MOFs have an overall long-term stability issue, both chemical and thermal. SciFinder search returns for patents filed for both MOFs and graphene from 2003-2016 (Fig. 12 left) show thatthe sum total of patents filed over the 14-year period is substantially less than those filed for graphene in 2016 alone.5 Industrial uses of MOFs are negligible, despite the fact that catalysis production is a $20 billion USD/yr industry, not to mention gas adsorption or separation, chemical
123 sensing applications, etc. Figure 12 (right) shows H2 adsorption isotherms by several MOFs and zeolite 13X, making the excitement generated by MOFs clear.123 37
Figure 12: MOF patents filed and H2 Isotherms for MOFs and Zeo13X (Left) SciFinder search hits for patents published on Metal-Organic Frameworks specifically under ‘Technology’ header and filtered by ‘Materials and Products’ or ‘Processes and Apparatus’ between 2003 and 2016. (Right) H2 Storage Capacities of several MOFs and Zeolite 13X.
However, none of the MOFs listed in Figure 12 (right) are used industrially nor available
for purchase outside specialty chemical outfitters for research, while zeolite 13X is industrially 38 produced for the petroleum industry and available to purchase by consumers on Alibaba.com.124-
125 Around two million tons of synthetic zeolites are industrially produced each year and used in over 30% of all global propylene production.126-127 As discussed earlier, graphene is limited by cost and quality of production.7 MOFs benefit from highly-scalable solvothermal synthesis methods. Scalable, solvent-free, mechanochemical synthesis has even been shown to produce several MOFs in high-purity, powder form.128-130 MOFs are stuck in academia because of a lack of stability.
There is a myriad of strategies being developed for improving stability in MOFs. A common approach to overcome water stability issues is to functionalize ligands to increase hydrophobicity. Studies on UiO-66 derivatives have shown that adding ethyl groups or trifluoromethyl groups to the ligands decreased the amount of water adsorbed by the MOFs.131
Further, a UiO-67 derivative replacing the biphenyldicarboxylate with perfluorinated azobenzenedicarboxylate was shown to be water stable.131 In a study between isostructural MOFs
[Co(isonicotinate)2]n and [Co(3-fluoroisonicotinate)2]n, the addition of fluorine increased thermal stability by 150 °C (from 250 °C to 400 °C) and showed improved adsorption properties for both
132 H2 and CO2 at 77 K.. The study is promising, but due to the difficulty in making isostructural analogues, the data are very limited on the exact effects of fluorination.
In an attempt to make a MOF that could be stable in both acidic and basic conditions, one research group synthesized a self-buffering ligand, with two carboxylic acid groups complimented by both an amino and a triazine groups to function as weak acids and bases respectively.133 The compound was shown to be stable from pH 1.5 to 12.5 with no loss to crystallinity or adsorption characteristics.133 39
In addition to functionalizing the body of a ligand, changing the binding site can also improve stability. Phosphonate monoesters (R-POOHOR’) in place of carboxylic acids (R-COOH) provide the same benefits of potentially bidentate O donors but gain an ester. The first reported
MOFs were [CuBDP-Et]n and [CuBDP-Me]n, where BDP is 1,4benzenediphosphonate bis(monoethyl and methyl esters), respectively, with the alkoxy groups over the metal center, sterically shielding it from water.134 The MOFs were stable when exposed to water and could be heated to 200 °C in air with no degradation, as measured by PXRD.135 In a more intentional investigation into the potential hindrance effect of the alkoxy group, CALF-25, a barium-MOF with an ethyl phosphonate monoester, maintained crystallinity and CO2 uptake after 24 hrs at 90%
RH and 80 °C, but lost crystallinity, exhibited evidence of a phase change, and partially dissolved when submerged in boiling water.135 While there is not yet experimental proof-of-concept, it is feasible that the ester could be functionalized as a catalytic active site, or to block pores to create a size-selective effect. Further, phosphonate monoesters address overall chemical stability more broadly than adding hydrophobicity. A limiting step in the production of more MOFs containing phosphonate monoester is the difficulty of the synthesis of the ligand and crystallization of the
136 MOF. Outside of the pair [CuBDP-Et] n and [CuBDP-Me]n, no isoreticular families of phosphonate monoester MOFs have been reported.134
40
1.4. Lanthanide-Metal-Organic Frameworks
Using lanthanides instead of transition metals may also increase stability. Transition metals typically coordinate up to six bonds with ligands. Lanthanides, on the other hand, typically coordinate eight to twelve, with as many as thirteen and as little as two being reported.137 As previously noted, an increase in coordination does not strictly mean an increase in stability.
However, there is a clear trend in the increased thermal and water stability of lanthanide metal- organic frameworks (Ln-MOFs) over transition-metal-metal-organic frameworks (TM-MOFs), which is often attributed to increased coordination.138 Direct experimental evidence is hampered by the lack of reported isostructural lanthanide and transition metal MOFs. A series of TM-MOFs vs Ln-MOFs crystallized with ligand pyridine-3,5-bis(phenyl-4-carboxylate) under similar conditions shows wide array of both metal-coordination environments and crystal systems, displayed in Table 2 on the following page.139 Neither coordination number nor geometry are indicators of stability, but the lanthanide compounds show significantly higher breakdown temperatures.139-140 Further, the ligand formed isostructural variants of erbium, ytterbium, and lutetium (all with comparable breakdown temperatures), indicating the isoreticular model applied to the lanthanides, but not transition metals.140 Lanthanides are the most chemically similar period in the periodic table, thus it is expected that isoreticular synthesis is more successful for rare earth elements than 3d metals.141
The rare-earths are even fungible enough to synthesize a rich variety of mixed-metal and doped MOFs, potentially leading to unique applications with tunable properties. Mixed-MOF system of transition metals are widely accomplished by post-synthetic modifications.142 In at least two publications, mixed-Ln-MOFs could be synthesized solvothermally by simply adjusting the 41 stoichiometry of the lanthanide precursors, resulting in isostructural variations with tunable
143-146 photoluminescence properties. Solvothermally synthesized co-Ln-MOF [(Yb1-x:Eux)(2,3- pyrazinedicarboxylate)2(OH) • H2O]n was found to exhibit fluorescent up-conversion , exhibiting
665, 540, and 518 nm emissions bands by 975 nm excitation, a unique property absent in the parent frameworks.146
Using lanthanides vs transition metals increases the availability of f-orbital electronic interactions, increasing the likelihood for chemical sensing mechanisms.138 Fluorescent up- conversion, the process of Anti-Stokes emission primarily through excited-state absorption or energy-transfer up-conversion, is well documented for lanthanide and actinide systems and has important applications in optical amplifiers, tunable lasers, and a diverse array of chemical and biological sensing assays.147 Reports of fluorescent up-conversion among Ln-MOFs are more common than those of TM-MOFs, despite the current predominance of TM-MOFs.148-151 So far, there have been only two readily accessible publications on upconverting TM-MOFs, and both exploit a well-studied energy-transfer up-converting donor-acceptor pair 9,10-diphenylantracene and platinum (II) octaethylporphyrin, modified as ligands.152-153 Lack of structural analogues makes direct comparison impossible, but neither [Zn3(BTC)2]n (MOF-3), [Cu3(BTC)2• 3H2O]n
(HKUST-1), nor [Fe(BTC)]n (Fe-MIL-100) have been observed to up-convert, while MOF
151, 154 [Nd(BTC)]n exhibits fluorescent emission at 450 nm by 580 nm excitation. Likewise,
[Nd(NDC)3• H2O]n has been shown to exhibit UV-Vis fluorescent up-conversion, but a thorough
155-156 study of the fluorescent properties of MOF [Zr(NDC)2]n found no up-conversion.
42
Table 2: Thermal Stability of Similar MOFs
43
MOF [Nd2(o-dibenzoic acid)3•2H2O]n was shown to exhibit up-converted emissions at 441,
424 and 370 nm by 580 nm excitation, but no up-conversion was exhibited by isostructural lanthanum (III) and praseodymium (III) frameworks.148 While these are just a limited few examples, fluorescent up-conversion in Ln-MOFs adds a feasible route to chemical sensing applications that is largely inaccessible to TM-MOFs.
Even for lanthanide frameworks that do not exhibit up-conversion, f f transitions in Ln3+ ions coupled with the high absorptivity of typical organic ligands leads to increased photoluminescence activity over 3d transition metals.157 We were intrigued by the relative simplicity of Ln-MOF synthesis and the possibility for exotic physicochemical properties that arise in these complex electronic systems. Our investigations with Ln-MOFs have largely focused on naphthalene-based ligands, which are cost-effective and thermally/chemically stable relative to the large branching phenols used to make ultra-porous structures. In addition to lanthanide-organic frameworks, we also investigated the properties of other novel lanthanide compounds, primarily looking at the optical characteristics.
The compositional effect of band gap resulting from Vergard’s law, the observation that lattice constants for an isostructural solid solution formed from isostructural precursors are approximately linearly dependent, has been studied for a variety of binary, ternary, and quaternary systems.158-160 Vergard’s law is not intended to predict properties from formations of different crystal systems, and does not take into account the effect of quantum confinement, defects, or dopants.158, 161-162 Compositional effects of band gap, then, is currently empirically based, since no cohesive framework exists that can inform a synthetic route to a desired electronic landscape. With 44 that philosophy, we explored the use of solvothermal, flux, and direct synthesis of lanthanide- transition metal oxysulfides and lanthanide-metalloid oxysulfides, in addition to Ln-MOFs.
45 CHAPTER TWO: THE SYNTHESIS AND PHOTOLUMINESCENCE PROPERTIES OF
[Ce(NO3)(NDC)•2DMA]n
Metal-organic frameworks (MOFs) are 2-to-3-dimension extensions of inorganic-organic coordination polymers. Composed of bridging ligands connecting a pseudo-infinite array of metal- centers, these materials are characteristically porous, consisting of molecular channels and apertures. Efforts to explore lanthanide-based structures in the in the rapidly expanding landscape of reported metal-organic frameworks (MOFs) has gain increasing attention due to their increased stability and complex electronic structures.138
2.1. Synthesis of [Ce(NO3)(NDC)•2DMA]n
Single-crystals of title compound [Ce(NO3)(NDC)•2DMA]n were synthesized and grown solvothermally by sonicating 2.0 mmol cerium (III) nitrate hexahydrate with 2.0 mmol 2,6- napthalenedicarboxylic acid (NDC) in 10.0 mL N,N’-dimethylacetamide (DMA) for 10 min, resulting in a colorless, opaque solution. The mixture was sealed in a PTFE-lined acid digestion vessel and placed in an oven at 100 °C for 48 hrs, after which it was cooled spontaneously in an oven to ambient temperature. After cooling, the acid digestion vessel was opened in ambient conditions, resulting in an amber solution over pastel-squash colored, transparent, polyhedral crystals. The resulting crystals were washed with approximately 100mL of DMA followed by
100mL of water while filter-drying. The mass of the dried crystalline solid obtained was typically 46 around 34(2) mg; yield based on crystallographic structure formula weight, discussed in the proceeding section, and the cerium nitrate precursor, was 3%. Various conditions were tested to optimize single-crystal formation for suitable analysis. Figure 13 summarizes the results of 72 trials varying concentration, time and temperature.
Figure 13: Varying synthetic conditions of [Ce(NO3)(NDC)•2DMA]n Single-crystal and powder X-ray diffraction reflections were collected on the as- synthesized product. For other tests, the product was vacuum-dried at 60 °C and 30 mtorr for 12-
24 hrs to remove solvent. The total mass recovered after vacuum drying was typically 26(6) mg and typically slightly less than the expected weight loss of the solvent, again indicated by crystallographic data, 24%.
2.2. Structural Characterization of [Ce(NO3)(NDC)•2DMA]n
Several crystals from a synthesis described as above were qualitatively chosen for single- crystal analysis. With a Bruker SMART CCD three-circle diffractometer with a monochromatized
Mo X-ray source, Kα = 0.71073 Å, and a nominal flux of 15 electrons per X-ray photon, the crystals 47 were screened using an Ewald rotation photograph and the acquisition of orientation matrices derived from 40 frames at 30 s/frame, all of which indicated an orthorhombic lattice. The figure of merit of the fit of reciprocal lattice parameters was used to identify the crystal most likely to diffract as it ought, and reflections were collected from theta angles 2.6847° to 29.2925° at -30 °C.
The crystal measured was approximately 400μm x 400μm x 300μm and the collection time for the hemisphere matrix, in which at least half of the Ewald sphere is measured, was 20.107 s/frame.
The program SADABS was used to apply absorption and Lorentz corrections to all reflections.163-
164 Non-hydrogen atomic coordinates were solved using traditional refinement methods , a riding model applied to generate hydrogen positions, and full matrix least-squares refinement on F2 was carried out using the SHELXTL suite.163, 165-166 Table 3 summarizes the data and relevant statistics.
A complete list of atomic positions can be found in the appendices in Table A1, bond lengths and angles in A2, and anisotropic displacement parameters in A3.
Figure 14 shows the 50% thermal ellipsoid probability plot of the asymmetric unit, as well as the primitive unit along the ‘a’ axis. The thermal ellipsoid plot was generated using Mercury, and the hydrogen atoms are not shown for clarity.167 The visualization of the unit cell was generated by Materials Studio.168 The numbering in Figure 14 corresponds to that in Tables A 1-4 in the appendices, in which atomic coordinates, anisotropic displacement parameters, bond lengths, and angles can be found. 48
Figure 14: 50% TELP plot and unit cell of [Ce(NO3)(NDC)•2DMA]n
(left) 50% probability plot of the asymmetric unit of [Ce(NO3)(NDC)]n and (right) primitive unit viewed along the ‘a’ axis. The asymmetric unit consists of 2,6-naphthalenedicarboxylate monochelated to a 7- coordinate cerium, or 8-coordinate if the nitrate nitrogen is counted. The oxygens from two solvent molecules N,N-dimethylacetamide coordinate to the cerium center. The monodentate carboxylate
Ce1-O1 distance is 2.46 Å, comparable to the monodentate Ce-O distance in an analogous
169 published MOF [Ce2(NDC)3]n, 2.47 Å. The carboxylate group bridges two cerium centers, which are separated by 4.34 Å The nitrate coordinates to the cerium in the expected motif in which two oxygens lie nearest the cerium and the Ce1-O7 distance is 2.62 Å, a typical distance for a nitrate in both analogous organic structures and inorganic structures.170-171 The distance between the nitrate nitrogen N1 and the cerium center is 3.04 Å.
49 Table 3: Crystallographic Refinement Details for [Ce(NO3)(NDC)•2DMA]n
Compound [Ce(NO3)(NDC)•2DMA]n
Empirical Formula C20H24CeN3O9 Formula Weight 590.54 Crystal System Orthorhombic Space Group Pbca a/Å 13.469(4) b/Å 18.364(6) c/Å 19.134(6) α/° 90 β/° 90 γ/° 90 V/Å3 4732(3) Z 8 -3 Dcalc/ g cm 2.149 μ/ mm-1 4.323 F(000) 2360 θ min, max /° 2.6847, 29.2925 tot, unique data 29980, 4152 observed data [I > 2σ(I)] 3854 a Rint (observed data [I > 2σ(I)]) 0.0584 b wR2 (all data) 0.157 GOFc 1.181 a 2 2 2 R1= Σ||Fo - Fc| |/|ΣFo | bwR2 =[Σ[w(Fo2-Fc2)2/Σ[w(Fo2)2]] 1/2 ; where w = 1/[σ2(Fo2) + (aP)2 + bP] , P = (Fo2 + 2Fc2)/3 cGOF =(Σw(Fo2-Fc2)2/(n-p))1/2, where n= total reflections and p is parameters
The overall structure consists of layered two-dimensional sheets along the (200) plane the
1 crystal staggered along the (002) glide plane by 9.57 Å ( the c-axis). The distance between(200) 2
1 planes separating the sheets is 6.73 Å ( the a- axis); a visualization by Materials Studio is shown 2 in Figures 15 and 16.168 The nearest neighbor between sheets is from a solvent hydrogen to a nitrate oxygen, H23C-O8 (and equivalent) length of 2.58 Å, which is too far to be a formal hydrogen 50 bond, but does make it likely that the solvent has some directing effect in the how the layers stack during crystallization.
Figure 15: Nearest distance between [Ce(NO3)(NDC)•DMA]n layers The nearest distance between (200) planes shown above in Angstroms is between a solvent hydrogen and a nitrate oxygen.
To check for phase purity between the single-crystal tested and the bulk sample, the powder diffraction pattern was collected on the bulk powder using a Bruker AXS D2 Phaser with a copper
X-ray source with Kα.= 1.54059994 Å and Kβ = 1.544398 Å. Figure 18 shows simulated powder data from the single-crystal structure solution, generated using Materials Studio, and the measured diffraction pattern.168
Qualitative analysis comparing the simulated powder pattern to a measured powder pattern suggests the bulk product is phase pure. The experimental powder diffraction and simulated powder diffraction are both shown in Figure 17. Figure 18 compares the as-synthesized powder diffraction pattern to that of the product after vacuum drying at 60 °C, 30 mtorr. The agreement in peak positions indicate significant structural changes do not occur upon removing solvent. 51
Figure 16: 2D layer stacking of [Ce(NO3)(NDC)]n
[Ce(NO3)]2[O2CC10H4]2 units link along the b-c plane making sheet. Solvent removed for clarity. The offset of the sheets is shown in the lower layer highlighted in yellow. The upper right image shows the (200) (blue) and (002) planes (red).
Figure 17: Experimental vs simulated diffraction of [Ce(NO3)(NDC)•2DMA]n (Upper) As-synthesized bulk product (Lower) Simulated product from single- crystal data 52
Figure 18: As-synthesized vs. vacuum-dried [Ce(NO3)(NDC)]n (Upper) As-synthesized bulk product and (Lower) Vacuum-dried product.
An FTIR spectrum was also measured for the bulk material after vacuum drying and compared to that of the ligand H2NDC (Fig 19). The broad O-H stretching frequency for a solid carboxylic acid around 3000 cm-1 is absent in the product, further verifying chelating by the ligand.172 The frequency at 2933 cm-1 in the product is an alkane stretch, expected to present in
2,6-naphthalenedicarboxylic acid, but could also be from unremoved DMA.172 The expected theoretical weight loss based on two DMA molecules per formula unit is 29.5% but was 28.3 % under the conditions used.172 The other frequency confirming the chelation is the shift in the
-1 -1 carbonyl peak of the H2NDC from 1685 cm to 1649 cm , a decrease in energy typical of π- backbonding coordination systems.173 53
Figure 19: FTIR spectra of [Ce(NO3)(NDC)]n and H2NDC
2.3. Stability of [Ce(NO3)(NDC)•2DMA]n
Thermal stability of [Ce(NO3)(NDC)•2DMA]n was tested on product sealed in an argon- flushed quartz tube at 0.75 mtorr, heated at a ramp of 200 °C per hour to 400 °C and held for one hour then cooled ambiently. As shown in Figure 20, the powder diffraction shows the predominant formation of a new phase, indicating that it is not thermally stable under the conditions tested.
54
Figure 20: PXRD thermal stability of [Ce(NO3)(NDC)•2DMA]n (Upper) As-synthesized bulk product (Lower) Product after heating at 400 °C for one hour
To test the pH stability of the material in water, 10. mg of vacuum-dried [Ce(NO3)(NDC)]n was dispersed into 100.0 mL 0.024 M HCl, measured pH of 1.6, and 0.024 M NaOH, measured pH of 12.3, and gently stirred at room temperature for one hour. Submersion under both basic and acidic conditions shows significant differences in intensities, but no significant differences in peak positions, indicating structural integrity is maintained within the time and pH tested (Fig. 21). 55
Figure 21: pH stability of [Ce(NO3)(NDC)]n
2.4. Photoluminescence Properties of [Ce(NO3)(NDC)]n
The photoluminescence properties of vacuum-dried [Ce(NO3)(NDC)]n were tested between 220 nm and 800 nm using a Shimadzu RF-6000 spectrofluorometer with a 150 W xenon- arc lamp excitation source. The solid-state total luminescence spectra, i.e. excitation wavelength vs emission wavelength vs intensity, of the bulk powder are shown in Figure 22. 56
Figure 22: Total luminescence spectra of [Ce(NO3)(NDC)]n The only area in Figure 21 of interest is the area around 250 nm excitation, 390 emission.
All other apparent intensities are instrumental artifacts. Slew-scanning resolved the primary absorption and emission wavelengths to be 243 nm and 393 nm, respectively, with a bandwidth of
3.0 nm for each measurement (Figure 23 top left).
[Ce(NO3)(NDC)]n exhibits a primary emission at 393 nm, with lower intensity emissions at 450 nm and 464 nm, similar emission bands to Ce(NO3)3•6H2O but a hypsochromic change in the Stokes shift from 280 to 243 nm in the absorption band. Relatively low intensities and inadequate spectrophotometric resolution preclude a peak analysis for the bands at 450 and 464 nm, but as shown in Figures 23 and 24, the emission spectrum is largely coincidental with that of solid-state Ce(NO3)3•6H2O. 57
Figure 23: Excitation and emission spectra of [Ce(NO3)(NDC)]n (Top left). Excitation spectra at 393 nm emission and emission spectra from 243 nm emission of [Ce(NO3)(NDC)]n. (Top right) Excitation spectra at 280 nm from 397 nm showing emissions around 398 nm, 451 nm, and 468 nm. (Bottom left) Image of powder [Ce(NO3)(NDC)]n emission from 243 nm excitation with a 10nm bandwidth from xenon arc source. (Bottom right) Excitation spectra of 2,6-naphthalenedicarboxylic acid at 405 nm and corresponding emission from 385 nm excitation. 58
Figure 24: [Ce(NO3)(NDC)]n fluorescent emissions similar to Ce(NO3)3•6H2O
The shift in absorption from 280 to 243 nm indicates that charge transfer is from the Ce3+
- to the NO3 constituents. CASTEP, a DFT-pseudopotentials computational method, was used to determine Hershfield charges on each atom and Mulliken bond orders using an LDA basis.174
Parallel computations were performed on [Ce(NO3)(NDC)]n and a reported cerium nitrate
175 structure, Ce(NO3)3•4H2O in Pbca for comparison.
Figure 25 shows the results of the analysis. For ease of comparison, normalizing the
Hirschfield charges on the nitrate group of each compound to -1, the Ce to NO3 charges are 6.4 to
-1 for the Ln-MOF and 46.6 to -1 for the nitrate salt, indicating the cerium-nitrate orbital overlap is significantly more antibonding in the Ln-than the nitrate salt. This increase in antibonding nature likely increases the LUMO. This is further reflected in the density of states, shown in Figure 26. 59
Figure 25: Hirshfield charges on [Ce(NO3)(NDC)]n
(Left) Hirshfield charges printed on the atoms of [Ce(NO3)(NDC)]n, with Mulliken bonding order printed on the bond and bond length printed just below the bond, in angstroms. (Right) Data printed accordingly, for Ce(NO3)3•4H2O. Figure 27 shows the truncated density of states from -10 eV to 2 eV; the inset shows the total density of states. The solid red line indicates the density of states for [Ce(NO3)(NDC)]n, and the blue dotted line for Ce(NO3)3•4H2O. Overlaid on the graph are lines representing possible
HOMO and LUMO, marked by an asterisk, states, derived from from similarities to the acquired spectra. The DOS indicates both the HOMO and the LUMO shift, which plausibly explains the hypsochromic shift as well. This is also in line with a qualitative analysis of the local geometries.
Figure 28 shows the local geometries side by side. Ln-MOF takes on a distorted square pyramidal shape [Ce(NO3)(NDC)]n which is anticipated by general frontier theory to have both a lower
HOMO and a higher LUMO than the square antiprism adopted by Ce(NO3)3•4H2O. Bandgap analysis using a more comprehensive k-grid is necessary to confirm these hypotheses. 60
Figure 26: DOS of [Ce(NO3)(NDC)]n and nitrate precursor
Figure 27: Geometric comparison of [Ce(NO3)(NDC)]n to Ce(NO3)3•4H2O
(Left) [Ce(NO3)(NDC)]n is a distorted square pyramid. (Right) Ce(NO3)3•4H2O is a distorted square antiprism.
Computational parameters for the Ce(NO3)3•4H2O can be found in Appendix B Table A
13, a full list of Mulliken bond orders in Table A 14, and a full list of Hirshfield charges in Table
A 14. Compuational parameters of [Ce(NO3)(NDC)]n can be found in Appendix B Table A 15, a full list of Mulliken bond orders in Table A 16, and a full list of Hirshfield charges in Table A 17. 61 CHAPTER THREE: THE SYNTHESIS AND PHOTOLUMINESCENCE PROPERTIES OF
[Nd(NO3)(NDC)•2DMA]n
Investigations into the synthesis and properties have shown metal-organic frameworks to be a promising class of material for application-guided design.176 This is largely a direct consequence of isoreticular synthesis, a generalizable reaction scheme in which ligands with desired properties can be used in place of similar ligands from an established synthesis.84 The periodicity of lanthanides makes the elemental family ideal for isoreticular synthesis.141 In a synthesis similar to that of [Ce(NO3)(NDC)]n, isostructural compound [Nd(NO3)(NDC)]n was synthesized by sonicating 1.8 mmol Nd(NO3)3•6H2O with 1.8mmol H2NDC in 10.0 mL DMA for
10 min to yield a colloidal, colorless solution which was then sealed in a 23 mL total-volume,
PTFE-lined, stainless steel acid digestion vessel and heated at 100 °C for 48 hrs. After heating, the vessel was cooled ambiently and opened in ambient conditions; transparent, lavender-melon hued plate crystals of compound were washed with 100 mL DMA and 100 mL water. A typical synthesis resulted in 20.5 mg of solid product, which is a yield of 2%. To evacuate solvent, the product was vacuum-dried at 60 °C, 20-30 mtorr for 12 hrs; typical weight loss after vacuum-drying was 31% while expected is 29%, slightly in excess due to transfer-loss.
3.1. Structural Characterization of [Nd(NO3)(NDC)•2DMA]n
Single-crystal selection was procedurally identical to that of [Ce(NO3)(NDC)•2DMA]n and reflections collected on the same instrument. The crystal measured was approximately 400 μm x 62 100 μm x 50 μm in size. Reflections were collected from theta angles 2.4097° to 29.22946° at -30
°C at 30.671 s/frame. Absorption and Lorentz corrections were applied using SADABS.163-164
Traditional refinement was used to generate a model for non-hydrogen coordinates, and a riding model applied to generate hydrogen positions.163, 166 A full matrix least-squares refinement on F2 was carried out using the SHELXTL suite.163, 165-166 The determined asymmetric unit, image generated by Mercury, is shown in Figure 29.177 A summary of the relevant statistics are shown in
Table 4, and a complete list of atomic positions can be found in the appendix in Table A 5, bond lengths and angles in A 6, and anisotropic displacement parameters in A 7.
Figure 28: 50% TELP plot of [Nd(NO3)(NDC)•2DMA]n
63 Table 4: Crystallographic Refinement Details for [Nd(NO3)(NDC)•2DMA]n
Compound [Nd(NO3)(NDC)•2DMA]n
Empirical Formula C20H24NdN3O9 Formula Weight 594.65 Crystal System Orthorhombic Space Group Pbca a/Å 13.583(3) b/Å 18.371(4) c/Å 19.039(4) α/° 90 β/° 90 γ/° 90 V/Å3 4751.0(2) Z 8 -3 Dcalc/ g cm 2.054 μ/ mm-1 4.374 F(000) 2376 θ min, max /° 2.4097, 29.2946 tot, unique data 31960, 4178 observed data [I > 2σ(I)] 4077 a Rint (observed data [I > 2σ(I)]) 0.0358 b wR2 (all data) 0.0684 GOFc 1.279 a 2 2 2 R1= Σ||Fo - Fc| |/|ΣFo | bwR2 =[Σ[w(Fo2-Fc2)2/Σ[w(Fo2)2]] 1/2 ; where w = 1/[σ2(Fo2) + (aP)2 + bP] , P = (Fo2 + 2Fc2)/3 cGOF =(Σw(Fo2-Fc2)2/(n-p))1/2, where n= total reflections and p is parameters
As in [Ce(NO3)(NDC)•2DMA]n, [Nd(NO3)(NDC)•2DMA]n is comprised of two- dimensional sheets stacked by one half the a-axis, shifted by a half primitive lattice along the b-c plane. Figure 30 shows the view along the a-axis, with the (200) Miller planes shown in blue and the second layer highlighted in yellow, shown without solvent for clarity. The graphics were generated using Materials Studio from the structure solution.168 64
Figure 29: [Nd(NO3)(NDC)]n layers viewed along the a-axis The IR spectrum was measured to further verify the presence of chelated 2,6- naphthalenedicarboxylic acid, check to see if DMA was removed, and look for unexpected functional groups. Bulk product was finely ground and vacuum-dried at 50 mtorr and 60 °C for 12 hrs then about 20 mg was ground into 1 g of dessicated KBr and pressed at 35000 psi. Similar to
-1 [Ce(NO3)(NDC)]n and shown in Figure 31, the broad O-H stretching mode at 3049 cm is absent, indicating the ligand chelates at the OH, as indicated by the single-crystal diffraction structure solution. Further, the carbonyl stretch is lowered in energy from 1685 to 1656 cm-1 due to π- backbonding interactions between the metal center and the chelated group. 65
Figure 30: FTIR spectra of [Nd(NO3)(NDC)]n and H2NDC To compare the structure of the measured crystal to bulk phase of the product, a simulated powder X-ray diffraction pattern was generated using Materials Studio.168 Figure 32 shows the diffraction patterns of the simulated and the as-synthesized sample.
As can be seen in Figure 32, peak positions and intensities are in very good agreement; further, no unexpected reflections or expected absences were observed in the powder, indicating that the single-crystal is representative of the bulk powder at room temperature. 66
Figure 31: Diffraction patterns of [Nd(NO3(NDC)•2DMA]n (Upper) As-synthesized bulk product and (Lower) simulated product determined from single-crystal data.
3.2. Stability of [Nd(NO3)(NDC)•2DMA]n
To evaluate thermal stability of the structure, ca. 50 mg powder [Nd(NO3)(NDC)•2DMA]n was placed in a crucible and heated in open air for one hour and the diffraction pattern measured between 13.0 and 20.0 °2θ. Figure 33 shows the patterns for 200 °C, 300 °C, and 400 °C.
The powder diffraction patterns of [Nd(NO3)(NDC)•2DMA]n after heating at the indicated temperature for one hour, as well as the expected reflections based on single-crystal data. Primary reflections are noted with the Miller indices. The (022), (202), (220), (023), and (222) planes are observed after each heating cycle, while the (040) spacing, the lowest measured intensity at room temperature, was not observed at 300 or 400 °C. By 300 °C, resolution between the (202) and 67 (220) reflections is lost with the instrumental parameters used and an unexpected phase with a spacing on an order of 4.69 Å has formed, indicated with a dotted line in Figure 33.
Figure 32: Thermal stability of [Nd(NO3)(NDC)•2DMA]n By 400 °C, an additional spacing on an order of 5.09 Å has also formed. The diffractions at 17.4° and 18.9° 2θ are not found in common neodymium (III) oxide structures P63/mmc or
Im3m, both of which exhibit more narrow spacings in the Nd-O planes and Nd-Nd planes.178 Too large to be oxidation of neodymium, the spacings are also inconsistent with known structures of
2,6-naphthalenedicarboxylic acid.179 Still, the formation indicates the structure has started to undergo a solid-state transformation at 300 °C, thus thermal stability is limited in air. Larger than expected spacings in neodymium oxides, the material very likely remains a neodymium-NDC complex. 68
3.3. Photoluminescence Properties of [Nd(NO3)(NDC)]n
The photoluminescence properties of vacuum-dried [Nd(NO3)(NDC)]n were tested between
220 nm and 800 nm using a Shimadzu RF-6000 spectrofluorometer with a 150 W xenon-arc lamp excitation source. The solid-state total luminescence spectra, i.e. excitation wavelength vs emission wavelength vs intensity, of the bulk powder is shown in Figure 34.
Figure 33: Total luminescence spectra of [Nd(NO3)(NDC)]n The primary absorption was found to occur at 296 nm with several emissions, the most intense of which is at 305 nm. The solid-state photoluminescence by 296 nm excitation is shown in Figure 35. Notably, there is a relatively large Stokes shifted emission at 748 nm, as well. The harmonics, amplified by reflection from measuring a solid, are labeled as such. 69
Figure 34: Solid-state emission of [Nd(NO3)(NDC)]n To test fluorescent quenching selectivity versus various common aromatic analytes, 3.0 mg of the material was dispersed into 1.0 mL DMF in a cuvette, then 200.0 μL of a 3 mM solution of analyte in DMF was added and the cuvette gently agitated. Emission was measured from 310 to
800 nm using an excitation wavelength of 297 nm, which was found to be the optimal excitation 70 wavelength of the material in DMF. Figure 36 shows the photoluminescence of [Nd(NO3)(NDC)]n dispersed in DMF.
Figure 35: Photoluminescence of [Nd(NO3)(NDC)]n in DMF The cuvette was then decanted and rinsed several times with dichloromethane to wash the material. Prior to adding analyte, fluorescence of the material dispersed in 1.0 mL DMF was 71 measured and original spectra observed within tolerance indicated by standard deviation bars in
Figure 37.
Figure 36: Aromatic fluorescent quenching of [Nd(NO3)(NDC)]n in DMF
As shown in Figure 37, the quenching efficiency of the analytes tested varies, emission peaks do not. Figure 38 shows the quenching efficiency at 358 nm by an excitation wavelength of 297
퐼0−퐼퐴 nm. Quenching efficiency is determined by 푥 100 where I0 is the fluorescence intensity of 퐼0
[Nd(NO3)(NDC)]n in DMF and IA is the fluorescence intensity of [Nd(NO3)(NDC)]n in DMF with
0.5 mM analyte. 72
Figure 37: Quenching efficiency of analytes in [Nd(NO3)(NDC)]n
Figure 38 shows benzene more efficiently quenched the fluorescence of [Nd(NO3)(NDC)]n in. Benzene was also found to have the most similar excitation and absorption spectra in the solvent, shown in Figure 39. Under the conditions tested, benzene and the Ln-MOF both have broad 358 nm absorption bands starting around 270 nm and peaking at 297 nm, and emissions at
309 nm and 324 nm. Benzene in DMF exhibits an emission at 347 nm, while [Nd(NO3)(NDC)]n exhibits an emission at 358 nm. The spectral similarities indicate comparable electronic energies, which facilitates efficient energy transfer, allowing for efficient quenching. The ground state energy of benzene in DMF is electronically accessible to the excited state of [Nd(NO3)(NDC)]n.
Pyrrole and pyridine both exhibit a similar, but markedly smaller, emissions at 347 nm by
297 nm excitation. The excitation at 358 nm an emission by 297 nm spectra are shown in Figure
The 358 nm absorption band for each is red shifted relative to both benzene and [Nd(NO3)(NDC)]n, 73 indicating the relative electronic energies are more dissimilar. This dissimilarity explains the decrease in quenching efficiency.
Having the appropriate absorption spectra may be a convenient way to screen analytes for potentially efficient fluorescent quenching by a MOF. Theoretically, analytes could be targeted knowing only the absorption and excitation wavelengths of the MOF. However, o-phenanthroline is the outlier. As shown in Figure 40, it shows no spectral overlap with [Nd(NO3)(NDC)]n but still has measurable quenching efficiency. This indicates the path of the electronic relaxation of the fluorophore is different for o-phenanthroline than the other analytes tested. It was initially thought a size exclusion may preclude significant quenching At 7 Å long, o-phenanthroline is the largest analyte tested. The largest pore aperture in [Nd(NO3)(NDC)]n is 15 Å, but is constricted to 7 Å by the staggered layers, so it was expected to quench less efficiently than smaller analytes. To explore this further, larger analytes need to be tested, as well as more small molecule with comparable photoluminescence characteristics to [Nd(NO3)(NDC)]n. 74
Figure 38: Photoluminescence of benzene and [Nd(NO3)(NDC)]n The excitation spectra were acquired at an emission of 358 nm and the emission spectra were acquired at an excitation of 297 nm. The benzene concentration was 50 mM in DMF, and the [Nd(NO3)(NDC)]n concentration was 3.0 mg/mL in DMF. For each spectra, the bandwidth was 3.0 nm and the scan rate was 60 nm/min. 75
Figure 39: Photoluminescence of organic analytes and [Nd(NO3)(NDC)]n As in Figure 36, The excitation spectra were acquired at an emission of 358 nm and the emission spectra were acquired at an excitation of 297 nm. The concentration of each analyte was50 mM in DMF, and the [Nd(NO3)(NDC)]n concentration was 3.0 mg/mL in DMF. For each spectra, the bandwidth was 3.0 nm and the scan rate was 60 nm/min.
76
CHAPTER FOUR: THE SYNTHESIS AND PHOTOLUMINESCENCE PROPERTIES OF
[Eu(NO3)(NDC)•2DMA]n
Early investigations into metal-organic frameworks typically focused on gas storage and separation, particularly for volatile compressed gasses.180 Hampered by lack of MOF stability115,117 and poor heats of adsorption characteristic of typical physisorption mechanisms123 metal-organic frameworks have not yet gained traction as industrially significant materials for gas storage or separation. Other promising applications include catalysis and chemical sensing, which is typically achieved via photoluminescence.181
As discussed in chapters 2 and 3, investigations into the properties of lanthanide-metal- organic frameworks are increasingly relevant. The unique properties of accessible f f electronic transitions increase the probability of viable sensing mechanisms.138 Further, the periodicity of lanthanides makes the metals optimal for isoreticular synthesis.
Continuing the trend from chapters 2 and 3, europium metal-organic framework
[Eu(NO3)(NDC)•2DMA]n was synthesized by sonicating 1.8 mmol Eu(NO3)3•6H2O with 1.8 mmol H2NDC in 10.0 mL DMA for 10 min to yield a colloidal, colorless solution which was then sealed in a 23 mL total-volume, PTFE-lined, stainless steel acid digestion vessel and heated at 100
°C for 48 hrs. After heating, the vessel was cooled ambiently and opened in ambient conditions; transparent, coral-peach-tinted crystals of compound were washed with 100 mL DMA and 100 mL water. A typical synthesis resulted in around 80 mg of solid product, a yield around 7%. To evacuate solvent, the product was vacuum-dried at 60 °C, 20-30 mtorr for 12 hrs; typical weight 77 loss after vacuum-drying was 25% while expected is 29%. Structural Characterization of
[Eu(NO3)(NDC)•2DMA]n
A single crystal was chosen for analysis in an identical procedure to that of the previous compounds
[Ce(NO3)(NDC)•2DMA]n and [Nd(NO3)(NDC)•2DMA]n. Reflections were measured using a three-circle Bruker SMART CCD platform diffractometers with a monochromatic Mo source, but a higher flux of 260 electrons per X-ray photon. Approximately 2500 frames between 2.8911° and
27.5254° theta were collected at 12.000 s/frame. Table 5 has a summary of the structure details and refinement statistics. A full table of atomic coordinates can be found in Table A 9, bond lengths and angles in Table A 10, anisotropic displacement parameters in Table A 11, and hydrogen coordinates in Table A 12 in Appendix A.
A 50% TELP plot of [Eu(NO3)(NDC)•2DMA]n is shown, without hydrogens, in Figure 41, generated by Mercury.177 Figure 42, visualized by Materials Studio,168 shows the two-dimensional
structural motif formed by [Eu(NO3)(NDC)•2DMA]n, from the base unit making. A full list of atomic coordinates can be found in Appendix A, Table A 9, bond angles and lengths in Table A
10, anisotropic displacement parameters, in Table A 11, and hydrogen coordinates in Table A 12.
Figure 40: 50% TELP plot of [Eu(NO3)(NDC)•2DMA]n 78
Figure 41: 2D layer stacking of [Eu(NO3)(NDC)]n
Isostructural to [Ce(NO3)(NDC)•2DMA]n and [Nd(NO3)(NDC)•2DMA]n,
[Eu(NO3)(NDC)•2DMA]n forms staggered 2D sheets separated by the(200) planes, which lie 6.80
Å apart. The construction of the layers is shown in Figure 42, sans solvent. [Eu(NO3)]2[O2CC10H4]2 units, shown on the left of Figure 39, link along the bc-plane making a sheet, shown in the center
(graphics produced using Materials Studio).168 Two such sheets stack along the a-axis; as shown in Figure 35, right. The lower sheet is highlighted yellow to illustrate the staggered position. The metal nitrate centers are staggered by the (022) planes, separated by 6.58 Å, and shown in Figure
39 as blue translucent planes on the right-most image.
To compare the bulk powder to the measured single-crystal, the powder X-ray diffraction pattern was collected on washed and ground as-synthesized powder. The results are shown in
Figure 43. The peak positions and intensities are in good agreement with the simulated powder data, generated by Materials Studio, so the bulk material can be assumed to be structurally identical to that determined by single-crystal diffraction.168 79 Table 5: Crystallographic Refinement Details for [Eu(NO3)(NDC)•2DMA]n
Compound [Eu(NO3)(NDC)•2DMA]n
Empirical Formula C20H24NdN3O9 Formula Weight 602.39 Crystal System Orthorhombic Space Group Pbca a/Å 13.597(3) b/Å 18.252(4) c/Å 19.011(4) α/° 90 β/° 90 γ/° 90 V/Å3 4718.1(18) Z 8 -3 Dcalc/ g cm 2.672 μ/ mm-1 5.983 F(000) 2400 θ min, max /° 2.8911, 27.5254 tot, unique data 88846, 4150 observed data [I > 2σ(I)] 3250 a Rint (observed data [I > 2σ(I)]) 0.0227 b wR2 (all data) 0.0685 GOFc 1.036 a 2 2 2 R1= Σ||Fo - Fc| |/|ΣFo | bwR2 =[Σ[w(Fo2-Fc2)2/Σ[w(Fo2)2]] 1/2 ; where w = 1/[σ2(Fo2) + (aP)2 + bP] , P = (Fo2 + 2Fc2)/3 cGOF =(Σw(Fo2-Fc2)2/(n-p))1/2, where n= total reflections and p is parameters
80
Figure 42: PXRD of [Eu(NO3)(NDC)•2DMA]n (Upper) As-synthesized bulk product (Lower) Simulated product from single- crystal data
4.1. Photoluminescence Properties of [Eu(NO3)(NDC)]n
The photoluminescence properties of [Eu(NO3)(NDC)]n were measured on bulk powder sample vacuum-dried at 20-30 mtorr and 60 °C for 12 hrs pressed between quartz slides on a
Shimadzu RF-6000 spectrofluorometer. Figure 41 shows the total luminescence spectra of the solid. The primary absorption band was found to be around 344 nm with an emission of 613 nm.
The excitation and emission spectra are shown in Figure 45, with an inset image of the emission. 81
Figure 43: Total luminescence spectra of [Eu(NO3)(NDC)]n 82
Figure 44: Photoluminescence of [Eu(NO3)(NDC)]n
4.2. Analysis of Aqueous Chromic Acid with [Eu(NO3)(NDC)]n
To test the viability of using [Eu(NO3)(NDC)]n in chemical sensing applications, the fluorescence was measured when the product was dispersed into solutions of chromic acid.
Chromic acid is a toxic and carcinogenic by-product from the industrial production of stainless steel.182-183 Most of the accessible upstream detection methods for chromic acid involve fractioning and concentrating, compounding the issue of monitoring and regulating produced waste water.182-
183 The inherent sensitivity of fluorescence coupled with the inverse proportionality between 83 concentration and signal make fluorescence quenching an ideal candidate for the trace-level detection of chromic acid, as well as other hexavalent chromium species.
To test fluorescence quenching of chromic acid in water by [Eu(NO3)(NDC)]n 2.0 mg of vacuum-dried product was dispersed into 1000.0 μL DMA, followed by 500.0 μL concentrations of chromic acid in water, the lowest measured being 9.04 μM. No new electronic transitions were noted, so the fluorescence was tested at the shift observed on the neat material. The results are shown in Figure 46.
Figure 45: H2CrO4(aq) fluorescence quenching of [Eu(NO3)(NDC)]n
[Eu(NO3)(NDC)]n is able to detect micromolar levels of chromic acid in water. The relationship between concentration and fluorescence is detailed in Figure 47. The rate constant from the exponential decay model was found to be 31800/M. 84
Figure 46: Fluorescence effect of [H2CrO4 (aq)] concentration in [Eu(NO3)(NDC)]n As shown in Figure 47, chromic acid exponentially quenches the fluorescence of
[Eu(NO3)(NDC)]n in water/DMA. To determine the degree of selectivity of the quenching behavior, aqueous nickel (II) species, another common industrial by-product of stainless steel production, were tested. 2.0 mg of vacuum-dried [Eu(NO3)(NDC)]n was dispersed into 1.0 mL solution with various concentrations of Ni2+ (aq) prepared from nickel (II) chloride and photoluminescence activity measured. No new electronic transitions were noted. The effect of the concentration on fluorescent emission from [Eu(NO3)(NDC)]n is shown in Figure 48. Figure 49 depicts the decay of the primary emission band, 613 nm, with respect to the concentration. Based on the rate of decay determined for each chromic acid and nickel (II), [Eu(NO3)(NDC)]n quenches chromic acid approximately seven million times more efficiently under the conditions used.
However, the Stoke’s shift behavior was not found to be selective. 85
2+ Figure 47: Ni (aq) fluorescence quenching of [Eu(NO3)(NDC)]n
2+ Figure 48: Fluorescence effect of [Ni ] concentration on [Eu(NO3)(NDC)]n 86 CHAPTER FIVE: EXPLORATORY SYNTHESIS OF LANTHANIDE-METALLOID COMPLEXES
FOR PHOTOCATALYSIS
The recognition that chlorination, the most commonly used disinfection process in water treatment, produces secondary toxins and mutagens has led to an increased interest in pursuing alternative methods for water purification.184 The most viable alternative that has been widely studied is the use of titanium dioxide as a photocatalyst for advanced oxidation processes, a mechanism by which highly reactive hydroxyl radicals catalytically generated by oxidants attack organic compounds in water, generally producing harmLess carboxylates or carbon dioxide.185
Photoenergy from impingent radiation creates an exciton pair.186 The band gap of the exciton pair for known titanium dioxide structures sit at the right relative energies to generate extremely reactive hydroxide radicals in water. 185-187 For pairs that have diffused to the surface prior to recombination, adsorbed oxygen can scavenge the electron forming an oxygen radical, which reacts with hydronium to form hydrogen peroxide, which gets oxidized by an exciton pair forming a hydroxyl radical and anion.186-187 In the valence band, the hole is able to oxidize water, forming hydrogen peroxide, which can again be oxidized to form hydroxyl radicals.186-187 Further, the hole formed also has enough energy to oxidize several organic groups directly, R + h+ R+, forming a reactive intermediate contributing to the degradation of the pollutant.186
The overall process is outlined in Figure 50. The hydroxyl radical has about twice the oxidative potential of chlorides and chlorates, allowing it to more completely oxidize a wider 87 variety of organic pollutants and toxins, and the reaction rates are several orders of magnitude higher.185 From a practical perspective, the radicals are produced using a solid catalyst, which can be extricated from water much easier than homogenous additives. The challenge has been finding a material with an optimal band gap.
Figure 49: Illustration of the catalytic photodegradation mechanism The band gap informs the photoenergy necessary to create the exciton pair driving the degradation process; an ideal band gap would be generally between 500 and 600 nm, where the surface irradiance of sunlight is approximately three times the irradiance below 400 nm.188
Titanium dioxide requires an intense UV source to practically treat wastewater. Figure 51 shows the average solar irradiance at 1.5 air mass at the surface of the Earth. Above 600 nm , the absorption coefficient of water becomes a limiting factor.189 It is also relevant that waste water typically has many absorbers and colloidal particles that drastically decrease the exposure of a catalyst to impingent radiation.
Further, net band gap is not a wholly useful metric in predicting catalytic photodegradation activity. Bulk rutile titanium dioxide has a band gap of 3.05 eV, or 406 nm, and bulk anatase titanium dioxide has a band gap of 3.26 eV, or 380 nm.190 However, anatase exhibits higher 88 catalytic activity than rutile due to an increased rate of oxygen adsorption in water.191 Another complicating factor is the difficulty in predicting the relative energies of the valence and conduction bands to those of the hydroxyl radicals in solution, which need to lie near each other in order for the energy transfer to generate the radical to be feasible.
Figure 50: Solar irradiance AM 1.5 reference There are innumerable, interconnected factors that influence the efficacy of a heterogeneous catalyst for water treatment. For a novel catalyst, predicting specific interactions with water, various pollutants, and the effect of pH and dissolved oxygen on the energies of the valence and conduction band require intimate knowledge of the structure and composition, as well as comprehensive computational models of the electronic structure, to understand the chemistry involved. It is no surprise, then, that while small steps have been achieved to optimize the photocatalytic activity of titanium dioxide in this context, there haven’t been results enabling 89 practical use. The search for new materials that can achieve this goal, then, falls on exploratory synthesis.
Lanthanides provide a good architecture for materials with complicated band structures, but notoriously form complexes with properties that are difficult to predict. Lanthanum (III) hydroxide is neither soluble nor toxic, making it a good candidate for water purification. However, hexagonal lanthanum (III) hydroxide, the primary bulk structure, has a large band gap of 5.5 eV.192
Intercalating with small band gap semiconductors such as germanium (II) sulfide, Eg = 1.67 eV, may add intermediate electronic states, allowing for otherwise inaccessible transitions. Herein the synthesis and characterization of germanium (II) sulfide intercalated lanthanum (III) hydroxide is investigated.
5.1. Synthesis and Characteristics of GeS-Intercalated La(OH)3
Solvothermal synthesis using thiourea is an interesting alternative use of traditional salt fluxes. In a standard atmosphere, thiourea predominantly melts at 180.2 °C, a significantly lower temperature than alkaline salts and most metals.193 By 222.1 °C about 80% of the total mass of thiourea has been shown to decompose into ammonia, isothiocyanic acid, and carbon disulfide per
193 the reaction 2SC(NH2)2(s) 2NH3(g) + H2NCN(g) + CS2 (g). Fabricating metal sulfides from oxide precursors using hydrogen sulfide gas is well known, and solvothermal synthesis using carbon disulfide and ammonia directly as reactive solvents for various metal oxides have been shown to result in interesting morphologies of metal sulfides.194-195 Thiourea has also been used to produce high-purity binary metal sulfides of novel morphologies, as well as completely novel quaternary compounds.36, 196 Further, in organic chemistry, thiourea and its derivatives are known to produce cyclic aminothiazoles under basic conditions.197 90 To synthesize novel quaternary sulfur-containing lanthanides, thiourea was investigated as a reactive flux between lanthanum hydroxide and germanium oxide. Expressly, 9.0 mmol lanthanum (III) hydroxide, 0.90 mmol of germanium(IV) oxide, and 18 mmol thiourea were ground by mortar and pestle to a fine consistent powder and dispensed into a 23 mL total-volume,
PTFE-lined, stainless-steel acid digestion vessel and heated for 120 hrs at 220 °C, then cooled spontaneously with the oven.
A variety of gray, yellow, and orange powders resulted, as well as transparent crystal growth along the top and upper sides of the PTFE-liner. The transparent crystals were collected for analysts, and the rest of the powder was thoroughly rinsed and filtered with water, then acetone, then hexanes. After washing and drying, 119 mg of a honey-mustard-eggshell colored solid remained, a seven percent yield by lanthanum.
5.2. Identification of GeS-Intercalated La(OH)3
The powder X-ray diffraction pattern was collected on a third generation Rigaku Miniflex diffractometer with a copper source, Kα = 1.540600 Å, Kβ =1.544398 Å, and is shown in Figure
52.
The peak positions and intensities are in good agreement, indicating the material synthesized
198 is a structural analogue of P 63/m La(OH)3. A noticeable difference however, is that the diffraction pattern of the product has significantly more noise in the baseline, indicating crystalline material on a bed of amorphous solid. Composition was determined using an Oxford Analytical
INCA energy dispersive X-ray spectroscopy system coupled to a TESCAN Vega II scanning electron microscope. The results of the point scans are shown in Figure 44 and Table 7. In Figure 91 53, Spot 1 in Table 6 corresponds to the left-most image, Spot 2 corresponds to the center image, and Spot 3 corresponds to the right-most image.
Figure 51: PXRD La(OH)3[GeS]0.1 The EDS data show that the primary constituents of the material are lanthanum, germanium oxygen and sulfur. Atomic percentages on oxygen in particular are not quantitative. Further, atomic percent measurements by EDS on powder is less reliable than on electronically smooth surfaces. The empirical formula was then determined by using the lanthanum to germanium ratio of each measurement, 10.33(5):1, and the germanium to sulfur ratio, 1.3(3):1, taken as 10 to 1 and
1 to 1 as integers respectively. 92
Figure 52: SEM micrographs and select spectra of La(OH)3[GeS]0.1 Germanium (II) sulfide has been shown to be the most thermodynamically stable germanium-sulfur complex at or near standard conditions.199 The powder diffraction data indicates that the predominant structure is that of hexagonal lanthanum (III) hydroxide. The empirical formula was inferred to be ten lanthanum (III) hydroxide units per one germanium (II) sulfide.
To determine whether the material was a solid solution or merely mixed powders, EDS elemental mapping was used. The results of the elemental mapping are shown in Figure 54, which indicate the solution was a homogenous mixture. 93 Table 6: EDS Analysis of La(OH)3[GeS]0.1
Spot 1 Spot 2 Spot 3
Element, Shell Atomic % Atomic % Atomic % Average Atomic %
O K 73.67 75.40 84.91 77.99
S K 1.59 1.21 1.35 1.38
Ge K 2.01 2.18 1.20 1.80
La L 21.73 21.21 12.54 18.83
La: Ge 11.31 9.73 10.45 10.33(5): 1
Ge:S 1.26 1.80 0.89 1.3(3):1
Figure 53: Elemental mapping of La(OH)3[GeS]0.1 The elemental mapping results indicate a thoroughly intercalated solid solution. The material can thus be characterized as La(OH)3[GeS]0.1. The crystalline side product was analyzed using singe-crystal diffraction and EDS and determined to be the C3N6H6 melamine compound.
Figure 55 shows a micrograph and EDS composition analysis, Table 7 shows crystallographic refinement data, and Figure 56 shows the 50% TELP plot, with hydrogens arbitrarily set to 0.15
Å radii, for the unit cell along the b-axis with a slight angle for perspective. The SHELXTL suite 94 was used for structural determination.163, 165 The TELP plot graphics were generated using
Mercury.177 Materials Studio was used for unit cell visualization.168
Figure 54: EDS spectrum of side-product melamine A 50 % TELP plot of the unit cell for the melamine side-product is shown in Figure 53 The decomposition of thiourea, SC(NH2) into cyclic C3N3(NH2)3 is further proof that the thiourea acts a reactive flux in the system. Though germanium oxide metathesis reactions with carbon disulfide have not been reported, a plausible reaction mechanism could proceed similarly to R2SnO substitution reactions.200 Germanium oxide complexes with the cyanamine breakdown product forming trimer [(CNNH2)2GeO]3 which metathesizes with three carbon disulfides to form three
COS and intermediate [(CNNH2)2GeS]3. Ammonia could then reduce the germanium (IV) species to germanium (II) sulfide and the cyano complex to the cyclic imine melamine. No comprehensive mechanistic studies have been carried out, though, and no other products were able to be isolated to help elucidate the formation of the product. Further, the thorough intercalation of the germanium
(II) sulfide into the lanthanum (III) hydroxide suggests that the nucleation of germanium (II) sulfide evenly distributed throughout the reaction, not isolated at the top. This necessitates either very fast kinetics and/or lanthanum involvement in the coordination of the reaction. 95
Figure 55: 50% TELP plot of melamine unit cell
96 Table 7: Crystallographic Refinement Details for Melamine Compound Melamine
Empirical Formula C3N6H6 Formula Weight 126.12 Crystal System Monoclinic Space Group P21/n a/Å 7.2762(13) b/Å 7.4722(14) c/Å 10.3354(19) α/° 90 β/° 108.522(3) γ/° 90 V/Å3 532.82(17) Z 3 -3 Dcalc/ g cm 0.393 μ/ mm-1 0.029 F(000) 198 θ min, max /° 3.023, 24.996 tot, unique data 3745, 929 observed data [I > 2σ(I)] 900 a Rint (observed data [I > 2σ(I)]) 0.0433 b wR2 (all data) 0.1273 GOFc 0.985 a 2 2 2 R1= Σ||Fo - Fc| |/|ΣFo | bwR2 =[Σ[w(Fo2-Fc2)2/Σ[w(Fo2)2]] 1/2 ; where w = 1/[σ2(Fo2) + (aP)2 + bP] , P = (Fo2 + 2Fc2)/3 cGOF =(Σw(Fo2-Fc2)2/(n-p))1/2, where n= total reflections and p is parameters
5.3. Band Gap Measurements
To determine the band gap, diffuse reflectance spectra were collected on flattened powder material between 220 and 900 nm using a barium (II) sulfate reference background on a Hitachi
FL-4500 spectrofluorometer with a xenon-arc source in synchronous scan mode at 60 nm/min, excitation and emission bandwidths of 2.5 nm, and an integration time of 500 μs with 700 V across 97 the photomultiplier tube. For comparison, the spectrum of anatase titanium dioxide was obtained in using an identical procedure. The spectra obtained are shown in Figure 54.
Figure 56: DRS spectrum of La(OH)3[GeS]0.1
The diffuse reflectance spectrum of La(OH)3[GeS]0.1 indicates it has an absorption onset at about 350 nm, roughly similar to TiO2(anatase), but much broader, stretching all the way to near
600 nm. To evaluate the band gap from the DRS data, the Kubelka-Munk function was used an
(1−푅)2 approximation of absorption coefficient, i.e. α ≈ F(R) = where R is the reflectance.201 A 2푅 direct band gap model that assumes parabolic-semiconductor electronic transitions in a crystalline
2 lattice in which electron momentum is conserved was used to quantify the band gap, i.e. (αhv) =
201-202 A(hv – Eg). The band gap Eg can then be directly determined by the intersection at the abscissa of the linear change in (F(R)hv)2 versus photon energy. 98 Figure 55 shows the experimental band gap of anatase titanium dioxide, which was found to be 3.5 eV, close to that of reported values of 3.44 eV determined by DRS,201 and reasonably deviates from 3.26 eV determined in solution by the Mott-Schottky method, which directly measures capacitance at the charge transfer layer and thus will account for more charge transfer mechanisms than DRS.190
Figure 57: Band gap of TiO2, anatase
The measured band gap of La(OH)3[GeS]0.1 is shown in Figure 56. The bandgap of
La(OH)3[GeS]0.1 was found to be 3.2 eV, or 387 nm. 99
Figure 58: Band gap of La(OH)3[GeS]0.1
5.4. Photocatalytic Activity of La(OH)3[GeS]0.1
To measure the effectiveness of La(OH)3[GeS]0.1 as a photodegradation catalyst, 5 mg of 300 mesh La(OH)3[GeS]0.1 was dispersed in to 100.0 mL a 4.0 mg/L aqueous methylene blue solution.
The solution was placed under a 100 W high-pressure mercury-vapor arc discharge lamp and gently stirred with a magnetic stir bar. A fan was used to keep the solution cool under the lamp.
Absorbance measurements were made in 5 min intervals.
As a reference, the measurement procedure was repeated for 21 nm average particle-size, polycrystalline titanium dioxide, 300 mesh lanthanum hydroxide, and with no catalyst. The results, as well as the spectral output of the light source used, are shown in Figure 57. 100
Figure 59: Photodegradation by La(OH)3[GeS]0.1
Figure 60: Exponential decay of methylene blue by La(OH)3[GeS]0.1 The decay rates indicated by an exponential decay fit indicate that the 21 nm polycrystalline titania 3.5x the photodegradation rate of La(OH)3[GeS]0.1 under the conditions 101 tested. Similar to the phenomenon that enhances the photoactivity of anatase relative to rutile titania, this could be due to the rate of oxygen adsorption on the surface of the catalyst, or simply a function of the accessible surface area of the catalyst to the solvent. Still, while lanthanides have been incorporated directly into titanium dioxide in efforts to tune the catalytic activity,
La(OH)3[GeS]0.1 represents a new direction for degradation of organic matter for water purification.203 Despite the compounding factors that affect the chemical mechanics of the system, this work shows the scope of materials investigated can extend beyond titanium dioxide complexes. 102 CHAPTER SIX: FUTURE WORKS AND CONCLUDING REMARKS
I started research on metal-organic frameworks around August 2013. I entered the field in a time when the landscape was changing faster than the perspectives. The second decade of the millennium saw researchers charting many paths toward novel materials, as well as redrawing the contour lines from the first decade or work. Using isoreticular synthesis as a heading, early efforts in the field focused on generalizable, predictable syntheses with tailored properties.77, 79 This gave solid-state chemists a glimpse into the deliberate methodologies that define bench-top organic chemistry, and led to a rich array of intriguing structures. Ultimately, though, this direction led stability and practicability astray.115, 135, 204-205 Structures were being intentionally synthesized with such large pores that simply removing the solvent threatened breakdown.67 The course- adjustments intended to guide MOFs toward marketable structures sacrificed much in terms of rational design. Exploratory synthesis is again often seen as the key to making an industrious MOF, just as any other solid.107, 135, 176, 206
Synthesizing this series of 2D lanthanide-naphtalenedicarboxylate networks is only the first leg of the journey. Herein, [Ln(NO3)(NDC)]n structures, where Ln is limited to Ce, Nd, and
Eu, were reported. Exploratory work is currently underway to complete the series from Y to Lu.
Crystals insufficient for indexing of potentially isostructural compounds from the series have been grown. Microcrystals of what may be [Sm(NO3)(NDC)•2DMA]n were grown by mixing 2.2 mmol of Sm(NO3)3•6H2O with 1.8 mmol NDCA and heating at 120 °C for 96 hrs. The powder diffraction 103 pattern suggests an isostructural compound to that of the [Ln(NO3)(NDC)•2DMA]n structures reported in Chapters 2 -4.
Figure 61: PXRD of [Sm(NO3)(NDC)•2DMA]n
Further, single-crystals of [Yb(NO3)(NDC)•2DMA] were successfully grown by desiccating all reagents and sealing the reaction under argon prior to synthesis. The structure refinement was carried out as reported in Chapters 2-3.163-166 A 50% TELP plot, generated by
Mercury, is shown in Figure 56.177 Refinement details and statistics are shown in Table 8. 104
Figure 62: 50% TELP plot of [Yb(NO3)(NDC)•2DMA]n
Table 8: Crystallographic Refinement Details for [Yb(NO3)(NDC)•2DMA]n
Compound [Yb(NO3)(NDC)•2DMA]n
Empirical Formula C20H24YbN3O9 Formula Weight 623.47 Crystal System Orthorhombic Space Group Pbca a/Å 13.5964(10) b/Å 18.1874(15) c/Å 19.0269(16) α/° 90 β/° 90 γ/° 90 V/Å3 4705.0(7) Z 8 -3 Dcalc/ g cm 1.923 μ/ mm-1 5.503 F(000) 2456 θ min, max /° 2.1550, 25.0000 tot, unique data 72169, 4138 observed data [I > 2σ(I)] 3044 a Rint (observed data [I > 2σ(I)]) 0.0366 b wR2 (all data) 0.1334 GOFc 0.978 a 2 2 2 R1= Σ||Fo - Fc| |/|ΣFo | bwR2 =[Σ[w(Fo2-Fc2)2/Σ[w(Fo2)2]] 1/2 ; where w = 1/[σ2(Fo2) + (aP)2 + bP] , P = (Fo2 + 2Fc2)/3 cGOF =(Σw(Fo2-Fc2)2/(n-p))1/2, where n= total reflections and p is parameters
105 The challenge to predict structures is incorporating new tools. A recent JACS study highlights the use of a neural network artificial intelligence learning program that analyzed 50,000 known structures and predicted about 2.7 million ternary compound candidates that are likely to be synthesizable.207 Advanced computation efforts may soon help us predict not only which structures can be made, how to make them, and what properties and interactions compounds may have.
The characterization presented of the solid-state photoluminescence behavior of the reported [Ln(NO3)(NDC)]n is far from comprehensive. Interesting interactions arise between chemical systems, not within. Interactions, like that of mercury with the hybrid ruthenium- bipyridine-bioMOF discussed in Section 1.3 are unpredictable; even if detailed physical information about the complex microstates that govern such a reaction were readily available, knowing to look for such information implies omniscience.111
Flukes and a posteriori are the primary drivers that transform pure science into applied science. The photoluminescence of the materials synthesized needs to be investigated much more thoroughly and imaginatively. Studies on MOFs and similar compounds have found innovative routes such as temperature-induced, partial-pressure-induced, and even isotope-induced selectivity. 110, 145, 208 This is the critical difference between having a map and traversing a path.
Metal-organic frameworks are at the frontiers of the materials sciences, carving a trail west.
However, no map includes the landmarks necessary to direct the synthesis of an industrially-viable structure, because no map can guide what features should be tested.
The interesting electronics of lanthanides are not the only path towards a new class of stable, practical MOFs. Increased correlation effects between electrons and phenomena arising 106 from spin-orbit interactions lead to unique properties among the 5d-block metals that could lead to entirely new avenues of chemical sensing such as spintronics or transient magnetic moments.209
The number of 5d-based MOFs are few compared to their 3d cousins, but iridium (III) complexes studied have already demonstrated induced slow-magnetic relaxation behavior, a potential sensing mechanism, as well as selective fluorescence.210
The synthesis of novel solids is necessary for the advancement of all sciences. Further, while investigating the underlying mechanics involved in the synthesis of most solids is inherently difficult, it is no less important than studying their properties. Endeavoring towards a comprehensive atlas guiding the synthesis of new materials with tailored properties is the onus and ambition of several fields, working simultaneously, and often parallel. Even more important than optimizing function for application, materials in the future must be integrated sustainably. In that regard, non-toxic catalysts made of Earth-abundant elements should play an important role in future investigations. Chemistry of the twenty-first century will have to be wholly smarter, starting with the materials we make, use, and unmake in order to avoid further lead contamination problems
211 or another plastic Great Pacific Garbage Patch.212
†Note on nomenclature: Though there is an active task force regarding the nomenclature of metal- organic frameworks, along with other coordination compounds, IUPAC has not yet established guidelines.213 Attempting to systematically name metal-organic framework compounds is onerous, accordingly IUPAC still encourages the use of “trivial names or nicknames based on their place of origin followed by a number.”213 Hence, many names start NU for Northwestern University, HKUST for Hong Kong University of Science and Technology, MIL for Materials Institute Lavoisier, UiO for University of Oslo, etc.
107 REFERENCES
1. Wallace, P. R., The Band Theory of Graphite. Physical Review 1947, 71 (9), 622-634.
2. Templeton, I. M.; MacDonald, D. K. C., The Electrical Conductivity and Current Noise of Carbon Resistors. Proceedings of the Physical Society. Section B 1953, 66 (8), 680.
3. Cheli, M.; Fiori, G.; Iannaccone, G., A Semianalytical Model of Bilayer-Graphene Field- Effect Transistor. IEEE Transactions on Electron Devices 2009, 56 (12), 2979-2986. 10.1109/TED.2009.2033419
4. Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A., Electric Field Effect in Atomically Thin Carbon Films. Science 2004, 306 (5696), 666.
5. SciFinder A CAS Solution. https://scifinder.cas.org/ (accessed March 18, 2018).
6. Graphene: The worldwide patent landscape in 2015. Office, U. I. P., Ed. UK Intellectual Property Office: Newport, United Kingdome, 2015.
7. Mohan, V. B.; Lau, K.-t.; Hui, D.; Bhattacharyya, D., Graphene-based materials and their composites: A review on production, applications and product limitations. Composites Part B: Engineering 2018, 142, 200-220. https://doi.org/10.1016/j.compositesb.2018.01.013
8. Lam, K. T.; Peck, Y. Z.; Lim, Z. H.; Liang, G. In Performance comparison of armchair- edged and nitrogen-doped zigzag-edged graphene nanoribbon schottky barrier field-effect transistors, The 4th IEEE International NanoElectronics Conference, 21-24 June 2011; 2011; pp 1-2.
9. Sk, M. M.; Yue, C. Y.; Jena, R. K., Synthesis of graphene/vitamin C template-controlled polyaniline nanotubes composite for high performance supercapacitor electrode. Polymer 2014, 55 (3), 798-805. https://doi.org/10.1016/j.polymer.2013.12.057
10. Pudikov, D.; Zhizhin, E.; Rybkin, A.; Rybkina, A.; Zhukov, Y.; Vilkov, O.; Shikin, A., Electronic structure of graphene on Ni(111) and Ni(100) surfaces. Physics of the Solid State 2016, 58 (12), 2550-2554. 10.1134/S106378341612026X 108 11. Rajagopal, R.; Kamaludeen, B. A.; Krishnan, R., Synthesis and Exploration of Graphene Bubbles for Supercapacitor Electrodes. Electrochimica Acta 2015, 180, 53-63. https://doi.org/10.1016/j.electacta.2015.08.087
12. Lui, C. H.; Li, Z.; Mak, K. F.; Cappelluti, E.; Heinz, T. F., Observation of an electrically tunable band gap in trilayer graphene. Nature Physics 2011, 7 (12), 944-947. 10.1038/nphys2102
13. DiSalvo, F. J., Solid-State Chemistry: A A Rediscovered Chemical Frontier. Science 1990, 247 (4943), 649.
14. Liu, Z. K.; Zhou, B.; Zhang, Y.; Wang, Z. J.; Weng, H. M.; Prabhakaran, D.; Mo, S. K.; Shen, Z. X.; Fang, Z.; Dai, X.; Hussain, Z.; Chen, Y. L., Discovery of a Three-Dimensional Topological Dirac Semimetal, Na<sub>3</sub>Bi. Science 2014, 343 (6173), 864.
15. Sankar, C. R.; Becker, A.; Assoud, A.; Kleinke, H., New Quaternary Chalcogenides, Tl18Pb2M7Q25 (M = Ti, Zr, and Hf; Q = S and Se): Crystal Structure, Electronic Structure, and Electrical Transport Properties. Inorganic Chemistry 2013, 52 (4), 1895-1900. 10.1021/ic3020699
16. Bednorz, J. G.; Müller, K. A., Possible highTc superconductivity in the Ba−La−Cu−O system. Zeitschrift für Physik B Condensed Matter 1986, 64 (2), 189-193. 10.1007/BF01303701
17. Tarascon, J.-M.; McKinnon, W.; Greene, L.; Hull, G.; Vogel; EM, Oxygen and rare-earth doping of the 90-K superconducting perovskite YBa 2 Cu 3 O 7− x. Physical Review B 1987, 36 (1), 226.
18. Tarascon, J. M.; Greene, L. H.; McKinnon, W. R.; Hull, G. W., Superconductivity at 90 K in a multiphase oxide of Y-Ba-Cu. Physical Review B 1987, 35 (13), 7115-7118.
19. Antipov, E. V.; Loureiro, S. M.; Chaillout, C.; Capponi, J. J.; Bordet, P.; Tholence, J. L.; Putilin, S. N.; Marezio, M., The synthesis and characterization of the HgBa2Ca2Cu3O8+δ and HgBa2Ca3Cu4O10+δ phases. Physica C: Superconductivity 1993, 215 (1), 1-10. https://doi.org/10.1016/0921-4534(93)90358-W
20. Chen, H.; Liu, P.-F.; Li, B.-X.; Lin, H.; Wu, L.-M.; Wu, X.-T., Experimental and theoretical studies on the NLO properties of two quaternary non-centrosymmetric chalcogenides: BaAg2GeS4 and BaAg2SnS4. Dalton Transactions 2018, 47 (2), 429-437. 10.1039/C7DT04178K 109 21. Zhu, M.; Tan, W.; Wu, Z.; Tao, X.-T.; Huang, B.; Xia, S.-Q., Sr4Cu25.37(18)Sb12 and Eu4Cu26.06(13)Sb12: Copper-Rich Antimonide Intermetallics with Cage Structure. Crystal Growth & Design 2018, 18 (3), 1722-1729. 10.1021/acs.cgd.7b01645
22. Huang, J.; Liu, R.; Liu, Y.; Hu, Y.; Chen, G.; Yan, C.; Tian, J.; Hu, B., Effect of fluxes on synthesis and luminescence properties of BaSi2O2N2:Eu2+ oxynitride phosphors. Journal of Rare Earths 2018, 36 (3), 225-230. https://doi.org/10.1016/j.jre.2017.07.005
23. Yu, Y.; Lundström, T., Synthesis and structure investigation of the new ternary boride (Cr0.80W0.20)3B4 and its analogues (Cr1 − xTMx)3B4 with TM = Mo or Ta. Journal of Alloys and Compounds 1995, 228 (2), 122-126. https://doi.org/10.1016/0925-8388(95)01896-4
24. Talako, T. L.; Sharafutdinov, M. R.; Grigor’eva, T. F.; Vorsina, I. A.; Barinova, A. P.; Lyakhov, N. Z., Production of Ni x Al y /Al2O3 composites using a combination of mechanical activation and self-propagating high-temperature synthesis. Combustion, Explosion, and Shock Waves 2009, 45 (6), 662. 10.1007/s10573-009-0082-9
25. Su, X.; Fu, F.; Yan, Y.; Zheng, G.; Liang, T.; Zhang, Q.; Cheng, X.; Yang, D.; Chi, H.; Tang, X.; Zhang, Q.; Uher, C., Self-propagating high-temperature synthesis for compound thermoelectrics and new criterion for combustion processing. Nat Commun 2014, 5, 4908. 10.1038/ncomms5908
26. Li, X.; Cai, W.; An, J.; Kim, S.; Nah, J.; Yang, D.; Piner, R.; Velamakanni, A.; Jung, I.; Tutuc, E.; Banerjee, S. K.; Colombo, L.; Ruoff, R. S., Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils. Science 2009, 324 (5932), 1312.
27. Chen, S.-M.; Lin, Y.-J., Controlled growth of MoS2 nanopetals on the silicon nanowire array using the chemical vapor deposition method. Journal of Crystal Growth 2018, 481, 18-22. https://doi.org/10.1016/j.jcrysgro.2017.10.028
28. Trad, K.; Carlier, D.; Croguennec, L.; Wattiaux, A.; Ben Amara, M.; Delmas, C., NaMnFe2(PO4)3 Alluaudite Phase: Synthesis, Structure, and Electrochemical Properties As Positive Electrode in Lithium and Sodium Batteries. Chemistry of Materials 2010, 22 (19), 5554- 5562. 10.1021/cm1015614
29. Jiang, S. P.; Duan, Y. Y.; Love, J. G., Fabrication of High-Performance Ni / Y 2 O 3 ZrO2 Cermet Anodes of Solid Oxide Fuel Cells by Ion Impregnation. Journal of The Electrochemical Society 2002, 149 (9), A1175-A1183. 110 30. Meyer, H. J., Solid state metathesis reactions as a conceptual tool in the synthesis of new materials. Dalton Transactions 2010, 39 (26), 5973-5982. 10.1039/C001031F
31. Lei, L.; He, D., Synthesis of GaN Crystals Through Solid-State Metathesis Reaction Under High Pressure. Crystal Growth & Design 2009, 9 (3), 1264-1266. 10.1021/cg801017h
32. Georgekutty, R.; Seery, M. K.; Pillai, S. C., A Highly Efficient Ag-ZnO Photocatalyst: Synthesis, Properties, and Mechanism. The Journal of Physical Chemistry C 2008, 112 (35), 13563-13570. 10.1021/jp802729a
33. Holmes, S. M.; Girolami, G. S., Sol−Gel Synthesis of KVII[CrIII(CN)6]·2H2O: A Crystalline Molecule-Based Magnet with a Magnetic Ordering Temperature above 100 °C. Journal of the American Chemical Society 1999, 121 (23), 5593-5594. 10.1021/ja990946c
34. Danks, A. E.; Hall, S. R.; Schnepp, Z., The evolution of 'sol-gel' chemistry as a technique for materials synthesis. Materials Horizons 2016, 3 (2), 91-112. 10.1039/C5MH00260E
35. Alias, S. S.; Ismail, A. B.; Mohamad, A. A., Effect of pH on ZnO nanoparticle properties synthesized by sol–gel centrifugation. Journal of Alloys and Compounds 2010, 499 (2), 231-237. https://doi.org/10.1016/j.jallcom.2010.03.174
36. Zhang, X.; Wang, Q.; Ma, Z.; He, J.; Wang, Z.; Zheng, C.; Lin, J.; Huang, F., Synthesis, Structure, Multiband Optical, and Electrical Conductive Properties of a 3D Open Cubic Framework Based on [Cu8Sn6S24]z− Clusters. Inorganic Chemistry 2015, 54 (11), 5301-5308. 10.1021/acs.inorgchem.5b00317
37. Lee, H.-W.; Muralidharan, P.; Ruffo, R.; Mari, C. M.; Cui, Y.; Kim, D. K., Ultrathin Spinel LiMn2O4 Nanowires as High Power Cathode Materials for Li-Ion Batteries. Nano Letters 2010, 10 (10), 3852-3856. 10.1021/nl101047f
38. Liang, W.; Babarao, R.; D’Alessandro, D. M., Microwave-Assisted Solvothermal Synthesis and Optical Properties of Tagged MIL-140A Metal–Organic Frameworks. Inorganic Chemistry 2013, 52 (22), 12878-12880. 10.1021/ic4024234
39. Lu, X.; Zhuang, Z.; Peng, Q.; Li, Y., Wurtzite Cu2ZnSnS4 nanocrystals: a novel quaternary semiconductor. Chemical Communications 2011, 47 (11), 3141-3143. 10.1039/C0CC05064D 111 40. Yaghi, O. M.; Li, H., Hydrothermal Synthesis of a Metal-Organic Framework Containing Large Rectangular Channels. Journal of the American Chemical Society 1995, 117 (41), 10401- 10402. 10.1021/ja00146a033
41. Bayat, O.; Khavandi, A. R.; Ghasemzadeh, R., Synthesis of TiCr2 intermetallic compound from mechanically activated starting powders via calcio-thermic co-reduction. Physics of Metals and Metallography 2017, 118 (5), 444-451. 10.1134/S0031918X17050039
42. Gomez-Yañez, C.; Benitez, C.; Balmori-Ramirez, H., Mechanical activation of the synthesis reaction of BaTiO3 from a mixture of BaCO3 and TiO2 powders. Ceramics International 2000, 26 (3), 271-277. https://doi.org/10.1016/S0272-8842(99)00053-X
43. James, S. L.; Adams, C. J.; Bolm, C.; Braga, D.; Collier, P.; Friscic, T.; Grepioni, F.; Harris, K. D. M.; Hyett, G.; Jones, W.; Krebs, A.; Mack, J.; Maini, L.; Orpen, A. G.; Parkin, I. P.; Shearouse, W. C.; Steed, J. W.; Waddell, D. C., Mechanochemistry: opportunities for new and cleaner synthesis. Chemical Society Reviews 2012, 41 (1), 413-447. 10.1039/C1CS15171A
44. Joo, S. H.; Park, J. Y.; Tsung, C.-K.; Yamada, Y.; Yang, P.; Somorjai, G. A., Thermally stable Pt/mesoporous silica core–shell nanocatalysts for high-temperature reactions. Nature Materials 2008, 8, 126. 10.1038/nmat2329 https://www.nature.com/articles/nmat2329#supplementary-information
45. Kanatzidis Mercouri, G.; Pöttgen, R.; Jeitschko, W., The Metal Flux: A Preparative Tool for the Exploration of Intermetallic Compounds. Angewandte Chemie International Edition 2005, 44 (43), 6996-7023. 10.1002/anie.200462170
46. Stein, A.; Keller, S. W.; Mallouk, T. E., Turning Down the Heat: Design and Mechanism in Solid-State Synthesis. Science 1993, 259 (5101), 1558.
47. Jeitschko, W.; Nowotny, H., Die Kristallstruktur von Ti3SiC2—ein neuer Komplexcarbid- Typ. Monatshefte für Chemie - Chemical Monthly 1967, 98 (2), 329-337. 10.1007/BF00899949
48. Vepřek, S., The search for novel, superhard materials. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 1999, 17 (5), 2401-2420. 10.1116/1.581977 112 49. Jeitschko, W.; Nowotny, H.; Benesovsky, F., Kohlenstoff-haltige ternre Phasen (Nb3Al2C und Ta3Al2C). Monatshefte fr Chemie 1963, 94 (1), 332-333. https://doi.org/10.1007/BF00900259
50. Etzkorn, J.; Ade, M.; Hillebrecht, H., Ta3AlC2 and Ta4AlC3 − Single-Crystal Investigations of Two New Ternary Carbides of Tantalum Synthesized by the Molten Metal Technique. Inorganic Chemistry 2007, 46 (4), 1410-1418. 10.1021/ic062231y
51. Bondioli, F.; Corradi, A. B.; Manfredini, T.; Leonelli, C.; Bertoncello, R., Nonconventional Synthesis of Praseodymium-Doped Ceria by Flux Method. Chemistry of Materials 2000, 12 (2), 324-330. 10.1021/cm990128j
52. Ropp R, C.; Carroll, B., Solid‐State Kinetics of LaAl11O18. Journal of the American Ceramic Society 2006, 63 (7‐8), 416-419. 10.1111/j.1151-2916.1980.tb10203.x
53. Munir, Z. A.; Anselmi-Tamburini, U., Self-propagating exothermic reactions: the synthesis of high-temperature materials by combustion. Materials Science Reports 1989, 3 (6), 279-365.
54. Yeh, C. L.; Ke, C. Y.; Chen, Y. C., In situ formation of TiB2/TiC and TiB2/TiN reinforced NiAl by self-propagating combustion synthesis. Vacuum 2018, 151, 185-188. https://doi.org/10.1016/j.vacuum.2018.02.024
55. Zhou, A.; Wang, C.-A.; Hunag, Y., Synthesis and mechanical properties of Ti3AlC2 by spark plasma sintering. Journal of Materials Science 2003, 38 (14), 3111-3115. 10.1023/A:1024777213910
56. Rodriguez Miguel, A.; Makhonin Nikolay, S.; Escriña Juan, A.; Borovinskava Inna, P.; Osendi María, I.; Barba Maria, F.; Iglesias Juan, E.; Moya José, S., Single crystal ß‐Si3N4 fibers obtained by self‐propagating high temperature synthesis**. Advanced Materials 2004, 7 (8), 745-747. 10.1002/adma.19950070815
57. Ani, M. H.; Kamarudin, M. A.; Ramlan, A. H.; Ismail, E.; Sirat, M. S.; Mohamed, M. A.; Azam, M. A., A critical review on the contributions of chemical and physical factors toward the nucleation and growth of large-area graphene. Journal of Materials Science 2018, 53 (10), 7095- 7111. 10.1007/s10853-018-1994-0 113 58. Shin, H.-J.; Yoon, S.-M.; Mook Choi, W.; Park, S.; Lee, D.; Yong Song, I.; Sung Woo, Y.; Choi, J.-Y., Influence of Cu crystallographic orientation on electron transport in graphene. Applied Physics Letters 2013, 102 (16), 163102. 10.1063/1.4802719
59. Shimizu, T.; Xie, T.; Nishikawa, J.; Shingubara, S.; Senz, S.; Gösele, U., Synthesis of Vertical High‐Density Epitaxial Si(100) Nanowire Arrays on a Si(100) Substrate Using an Anodic Aluminum Oxide Template. Advanced Materials 2007, 19 (7), 917-920. 10.1002/adma.200700153
60. Parkin, I. P., Solid state metathesis reaction for metal borides, silicides, pnictides and chalcogenides: ionic or elemental pathways. Chemical Society Reviews 1996, 25 (3), 199-207. 10.1039/CS9962500199
61. Martinolich, A. J.; Neilson, J. R., Pyrite Formation via Kinetic Intermediates through Low- Temperature Solid-State Metathesis. Journal of the American Chemical Society 2014, 136 (44), 15654-15659. 10.1021/ja5081647
62. Hench, L. L.; West, J. K., The sol-gel process. Chemical Reviews 1990, 90 (1), 33-72. 10.1021/cr00099a003
63. Sui, R.; Charpentier, P., Synthesis of Metal Oxide Nanostructures by Direct Sol–Gel Chemistry in Supercritical Fluids. Chemical Reviews 2012, 112 (6), 3057-3082. 10.1021/cr2000465
64. Gesser, H. D.; Goswami, P. C., Aerogels and related porous materials. Chemical Reviews 1989, 89 (4), 765-788. 10.1021/cr00094a003
65. Ward, D. A.; Ko, E. I., Preparing Catalytic Materials by the Sol-Gel Method. Industrial & Engineering Chemistry Research 1995, 34 (2), 421-433. 10.1021/ie00041a001
66. Lou, W.; Chen, M.; Wang, X.; Liu, W., Novel Single-Source Precursors Approach to Prepare Highly Uniform Bi2S3 and Sb2S3 Nanorods via a Solvothermal Treatment. Chemistry of Materials 2007, 19 (4), 872-878. 10.1021/cm062549o
67. Farha, O. K.; Eryazici, I.; Jeong, N. C.; Hauser, B. G.; Wilmer, C. E.; Sarjeant, A. A.; Snurr, R. Q.; Nguyen, S. T.; Yazaydın, A. Ö.; Hupp, J. T., Metal–Organic Framework Materials with Ultrahigh Surface Areas: Is the Sky the Limit? Journal of the American Chemical Society 2012, 134 (36), 15016-15021. 10.1021/ja3055639 114 68. Cundy, C. S.; Cox, P. A., The Hydrothermal Synthesis of Zeolites: History and Development from the Earliest Days to the Present Time. Chemical Reviews 2003, 103 (3), 663- 702. 10.1021/cr020060i
69. Laudise, R. A., Hydrothermal Synthesis of Crystals. Chemical & Engineering News Archive 1987, 65 (39), 30-43. 10.1021/cen-v065n039.p030
70. Christensen, A. N.; Rasmussen, S. E., Hydrothermal Preparation of Compounds of the Type ABO3 and AB2O4. Acta Chemica Scandinavica 1963, 17, 845. 10.3891/acta.chem.scand.17-0845
71. Komarneni, S.; Li, Q.; Stefansson, K. M.; Roy, R., Microwave-hydrothermal processing for synthesis of electroceramic powders. Journal of Materials Research 1993, 8 (12), 3176-3183. 10.1557/JMR.1993.3176
72. Eckert James, O.; Hung‐Houston Catherine, C.; Gersten Bonnie, L.; Lencka Malgorzata, M.; Riman Richard, E., Kinetics and Mechanisms of Hydrothermal Synthesis of Barium Titanate. Journal of the American Ceramic Society 2005, 79 (11), 2929-2939. 10.1111/j.1151- 2916.1996.tb08728.x
73. Walton, R. I.; Millange, F.; Smith, R. I.; Hansen, T. C.; O'Hare, D., Real Time Observation of the Hydrothermal Crystallization of Barium Titanate Using in Situ Neutron Powder Diffraction. Journal of the American Chemical Society 2001, 123 (50), 12547-12555. 10.1021/ja011805p
74. Niederberger, M.; Pinna, N.; Polleux, J.; Antonietti, M., A General Soft‐Chemistry Route to Perovskites and Related Materials: Synthesis of BaTiO3, BaZrO3, and LiNbO3 Nanoparticles. Angewandte Chemie International Edition 2004, 43 (17), 2270-2273. 10.1002/anie.200353300
75. Niederberger, M.; Garnweitner, G., Organic Reaction Pathways in the Nonaqueous Synthesis of Metal Oxide Nanoparticles. Chemistry – A European Journal 2006, 12 (28), 7282- 7302. 10.1002/chem.200600313
76. Feng, P.; Bu, X., Hydrothermal syntheses and structural characterization of zeolite analogue compounds based on cobalt. Nature 1997, 388 (6644), 735.
77. Yaghi, O. M.; Li, H.; Davis, C.; Richardson, D.; Groy, T. L., Synthetic Strategies, Structure Patterns, and Emerging Properties in the Chemistry of Modular Porous Solids. Accounts of Chemical Research 1998, 31 (8), 474-484. 10.1021/ar970151f 115 78. Santoro, A.; Mighell, A. D.; Reimann, C. W., The crystal structure of a 1:1 cupric nitrate- pyrazine complex Cu(NO3)2.(C4N2H4). Acta Crystallographica Section B 1970, 26 (7), 979-984. doi:10.1107/S056774087000345X
79. Janiak, C., Functional Organic Analogues of Zeolites Based on Metal–Organic Coordination Frameworks. Angewandte Chemie International Edition in English 1997, 36 (13‐ 14), 1431-1434. doi:10.1002/anie.199714311
80. Yaghi, O. M.; O'Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J., Reticular synthesis and the design of new materials. Nature 2003, 423, 705. 10.1038/nature01650
81. Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A. Ö.; Snurr, R. Q.; O’Keeffe, M.; Kim, J.; Yaghi, O. M., Ultrahigh Porosity in Metal-Organic Frameworks. Science 2010, 329 (5990), 424.
82. O’Keeffe, M.; Peskov, M. A.; Ramsden, S. J.; Yaghi, O. M., The Reticular Chemistry Structure Resource (RCSR) Database of, and Symbols for, Crystal Nets. Accounts of Chemical Research 2008, 41 (12), 1782-1789. 10.1021/ar800124u
83. Zhang, J.; Wojtas, L.; Larsen, R. W.; Eddaoudi, M.; Zaworotko, M. J., Temperature and Concentration Control over Interpenetration in a Metal−Organic Material. Journal of the American Chemical Society 2009, 131 (47), 17040-17041. 10.1021/ja906911q
84. Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; Keeffe, M.; Yaghi, O. M., Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage. Science 2002, 295 (5554), 469.
85. Song, F.; Wang, C.; Falkowski, J. M.; Ma, L.; Lin, W., Isoreticular Chiral Metal−Organic Frameworks for Asymmetric Alkene Epoxidation: Tuning Catalytic Activity by Controlling Framework Catenation and Varying Open Channel Sizes. Journal of the American Chemical Society 2010, 132 (43), 15390-15398. 10.1021/ja1069773
86. Aerts, A.; Kirschhock, C. E. A.; Martens, J. A., Methods for in situ spectroscopic probing of the synthesis of a zeolite. Chemical Society Reviews 2010, 39 (12), 4626-4642. 10.1039/B919704B
116 87. Rood, J. A.; Boggess, W. C.; Noll, B. C.; Henderson, K. W., Assembly of a Homochiral, Body-Centered Cubic Network Composed of Vertex-Shared Mg12 Cages: Use of Electrospray Ionization Mass Spectrometry to Monitor Metal Carboxylate Nucleation. Journal of the American Chemical Society 2007, 129 (44), 13675-13682. 10.1021/ja074558j
88. Shekhah, O.; Wang, H.; Zacher, D.; Fischer Roland , A.; Wöll, C., Growth Mechanism of Metal–Organic Frameworks: Insights into the Nucleation by Employing a Step‐by‐Step Route. Angewandte Chemie International Edition 2009, 48 (27), 5038-5041. 10.1002/anie.200900378
89. Millange, F.; Medina Manuela , I.; Guillou, N.; Férey, G.; Golden Kathryn , M.; Walton Richard , I., Time‐Resolved In Situ Diffraction Study of the Solvothermal Crystallization of Some Prototypical Metal–Organic Frameworks. Angewandte Chemie International Edition 2010, 49 (4), 763-766. 10.1002/anie.200905627
90. Ahnfeldt, T.; Stock, N., Synthesis of isoreticular CAU-1 compounds: effects of linker and heating methods on the kinetics of the synthesis. CrystEngComm 2012, 14 (2), 505-511. 10.1039/C1CE05956D
91. Niekiel, F.; Ackermann, M.; Guerrier, P.; Rothkirch, A.; Stock, N., Aluminum-1,4- cyclohexanedicarboxylates: High-Throughput and Temperature-Dependent in Situ EDXRD Studies. Inorganic Chemistry 2013, 52 (15), 8699-8705. 10.1021/ic400825b
92. de Moor, P.-P. E.; Beelen, T. P.; van Santen, R. A., In situ observation of nucleation and crystal growth in zeolite synthesis. A small-angle X-ray scattering investigation on Si-TPA-MFI. The Journal of Physical Chemistry B 1999, 103 (10), 1639-1650.
93. Hall, S., Space-group notation with an explicit origin. Acta Crystallographica Section A 1981, 37 (4), 517-525. doi:10.1107/S0567739481001228
94. Van Vleet, M. J.; Weng, T.; Li, X.; Schmidt, J. R., In Situ, Time-Resolved, and Mechanistic Studies of Metal–Organic Framework Nucleation and Growth. Chemical Reviews 2018. 10.1021/acs.chemrev.7b00582
95. Yazaydın, A. Ö.; Snurr, R. Q.; Park, T.-H.; Koh, K.; Liu, J.; LeVan, M. D.; Benin, A. I.; Jakubczak, P.; Lanuza, M.; Galloway, D. B.; Low, J. J.; Willis, R. R., Screening of Metal−Organic Frameworks for Carbon Dioxide Capture from Flue Gas Using a Combined Experimental and Modeling Approach. Journal of the American Chemical Society 2009, 131 (51), 18198-18199. 10.1021/ja9057234 117 96. Wilmer, C. E.; Leaf, M.; Lee, C. Y.; Farha, O. K.; Hauser, B. G.; Hupp, J. T.; Snurr, R. Q., Large-scale screening of hypothetical metal-organic frameworks. Nature Chemistry 2012, 4 (2), 83-89. 10.1038/nchem.1192
97. Züttel, A., Hydrogen storage methods. Naturwissenschaften 2004, 91 (4), 157-172. 10.1007/s00114-004-0516-x
98. Target Explanation Document: Onboard Hydrogen Storage of Light-Duty Fuel Cell Vehicles. Energy, U. S. D. o., Ed. U.S. Department of Energy: 2017; pp 1-19.
99. Materials-Based Hydrogen Storage. https://www.energy.gov/eere/fuelcells/materials- based-hydrogen-storage (accessed March 29, 2018).
100. Hamilton, C. W.; Baker, R. T.; Staubitz, A.; Manners, I., B-N compounds for chemical hydrogen storage. Chemical Society Reviews 2009, 38 (1), 279-293. 10.1039/B800312M
101. Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.; Kim, J.; Keeffe, M.; Yaghi, O. M., Hydrogen Storage in Microporous Metal-Organic Frameworks. Science 2003, 300 (5622), 1127.
102. Dincǎ, M.; Dailly, A.; Liu, Y.; Brown, C. M.; Neumann, D. A.; Long, J. R., Hydrogen Storage in a Microporous Metal−Organic Framework with Exposed Mn2+ Coordination Sites. Journal of the American Chemical Society 2006, 128 (51), 16876-16883. 10.1021/ja0656853
103. Farha, O. K.; Özgür Yazaydın, A.; Eryazici, I.; Malliakas, C. D.; Hauser, B. G.; Kanatzidis, M. G.; Nguyen, S. T.; Snurr, R. Q.; Hupp, J. T., De novo synthesis of a metal-organic framework material featuring ultrahigh surface area and gas storage capacities. Nature Chemistry 2010, 2 (11), 944-948. 10.1038/nchem.834
104. Colón, Y. J.; Fairen-Jimenez, D.; Wilmer, C. E.; Snurr, R. Q., High-Throughput Screening of Porous Crystalline Materials for Hydrogen Storage Capacity near Room Temperature. The Journal of Physical Chemistry C 2014, 118 (10), 5383-5389. 10.1021/jp4122326
105. Zhou, H.; Liu, X.; Zhang, J.; Yan, X.; Liu, Y.; Yuan, A., Enhanced room-temperature hydrogen storage capacity in Pt-loaded graphene oxide/HKUST-1 composites. International Journal of Hydrogen Energy 2014, 39 (5), 2160-2167. https://doi.org/10.1016/j.ijhydene.2013.11.109 118 106. Guo, Y.; Feng, X.; Han, T.; Wang, S.; Lin, Z.; Dong, Y.; Wang, B., Tuning the Luminescence of Metal–Organic Frameworks for Detection of Energetic Heterocyclic Compounds. Journal of the American Chemical Society 2014, 136 (44), 15485-15488. 10.1021/ja508962m
107. Wang, M.-S.; Guo, S.-P.; Li, Y.; Cai, L.-Z.; Zou, J.-P.; Xu, G.; Zhou, W.-W.; Zheng, F.- K.; Guo, G.-C., A Direct White-Light-Emitting Metal−Organic Framework with Tunable Yellow- to-White Photoluminescence by Variation of Excitation Light. Journal of the American Chemical Society 2009, 131 (38), 13572-13573. 10.1021/ja903947b
108. Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T., Luminescent metal-organic frameworks. Chemical Society Reviews 2009, 38 (5), 1330-1352. 10.1039/B802352M
109. Nagarkar, S. S.; Desai, A. V.; Ghosh, S. K., A fluorescent metal-organic framework for highly selective detection of nitro explosives in the aqueous phase. Chemical Communications 2014, 50 (64), 8915-8918. 10.1039/C4CC03053B
110. Shustova, N. B.; Cozzolino, A. F.; Reineke, S.; Baldo, M.; Dincă, M., Selective Turn-On Ammonia Sensing Enabled by High-Temperature Fluorescence in Metal–Organic Frameworks with Open Metal Sites. Journal of the American Chemical Society 2013, 135 (36), 13326-13329. 10.1021/ja407778a
111. Lin, X.; Luo, F.; Zheng, L.; Gao, G.; Chi, Y., Fast, Sensitive, and Selective Ion-Triggered Disassembly and Release Based on Tris(bipyridine)ruthenium(II)-Functionalized Metal–Organic Frameworks. Analytical Chemistry 2015, 87 (9), 4864-4870. 10.1021/acs.analchem.5b00391
112. Wu, C.-D.; Hu, A.; Zhang, L.; Lin, W., A Homochiral Porous Metal−Organic Framework for Highly Enantioselective Heterogeneous Asymmetric Catalysis. Journal of the American Chemical Society 2005, 127 (25), 8940-8941. 10.1021/ja052431t
113. Zhang, F.-Y.; Yip, C.-W.; Cao, R.; Chan, A. S., Enantioselective addition of diethylzinc to aromatic aldehydes catalyzed by Ti (BINOL) complex. Tetrahedron: Asymmetry 1997, 8 (4), 585- 589.
114. Gupta, A. K.; De, D.; Tomar, K.; Bharadwaj, P. K., A Cu(ii) metal-organic framework with significant H2 and CO2 storage capacity and heterogeneous catalysis for the aerobic oxidative amination of C(sp3)-H bonds and Biginelli reactions. Dalton Transactions 2018, 47 (5), 1624- 1634. 10.1039/C7DT04006G 119 115. Kaye, S. S.; Dailly, A.; Yaghi, O. M.; Long, J. R., Impact of Preparation and Handling on the Hydrogen Storage Properties of Zn4O(1,4-benzenedicarboxylate)3 (MOF-5). Journal of the American Chemical Society 2007, 129 (46), 14176-14177. 10.1021/ja076877g
116. Panella, B.; Hirscher, M., Hydrogen Physisorption in Metal–Organic Porous Crystals. Advanced Materials 2005, 17 (5), 538-541. 10.1002/adma.200400946
117. Li, Y.; Yang, R. T., Gas Adsorption and Storage in Metal−Organic Framework MOF-177. Langmuir 2007, 23 (26), 12937-12944. 10.1021/la702466d
118. Férey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surblé, S.; Margiolaki, I., A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area. Science 2005, 309 (5743), 2040.
119. Gomes Silva, C.; Luz, I.; Llabrés i Xamena, F. X.; Corma, A.; García, H., Water Stable Zr–Benzenedicarboxylate Metal–Organic Frameworks as Photocatalysts for Hydrogen Generation. Chemistry - A European Journal 2010, 16 (36), 11133-11138. 10.1002/chem.200903526
120. DeCoste, J. B.; Peterson, G. W.; Jasuja, H.; Glover, T. G.; Huang, Y.-g.; Walton, K. S., Stability and degradation mechanisms of metal-organic frameworks containing the Zr6O4(OH)4 secondary building unit. Journal of Materials Chemistry A 2013, 1 (18), 5642-5650. 10.1039/C3TA10662D
121. Hailian, L.; Eddaoudi, Design and synthesis of an exceptionally stable and highly porous metal-organic framework. Nature 1999, 402 (6759), 276.
122. Park, K. S.; Ni, Z.; Côté, A. P.; Choi, J. Y.; Huang, R.; Uribe-Romo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M., Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proceedings of the National Academy of Sciences 2006, 103 (27), 10186.
123. Czaja, A. U.; Trukhan, N.; Muller, U., Industrial applications of metal-organic frameworks. Chemical Society Reviews 2009, 38 (5), 1284-1293. 10.1039/B804680H
124. Sylobead adsorbents for process applications. Davison, G. a. G., Ed. studiohauck: Cambridge, MA 02140, USA, 2010. 120 125. Alibaba. https://www.alibaba.com/product-detail/Competitive-Price-Oxygen-Generator- Air-Drying_60603705190.html?spm=a2700.7724857.main07.7.4e5c2d07Z4os69&s=p (accessed 04/09/2018).
126. Bellussi, G.; Pollesel, P., Industrial applications of zeolite catalysis: production and uses of light olefins. In Studies in Surface Science and Catalysis, Čejka, J.; Žilková, N.; Nachtigall, P., Eds. Elsevier: 2005; Vol. 158, pp 1201-1212.
127. Yilmaz, B.; Müller, U., Catalytic Applications of Zeolites in Chemical Industry. Topics in Catalysis 2009, 52 (6), 888-895. 10.1007/s11244-009-9226-0
128. Kandiah, M.; Nilsen, M. H.; Usseglio, S.; Jakobsen, S.; Olsbye, U.; Tilset, M.; Larabi, C.; Quadrelli, E. A.; Bonino, F.; Lillerud, K. P., Synthesis and Stability of Tagged UiO-66 Zr-MOFs. Chemistry of Materials 2010, 22 (24), 6632-6640. 10.1021/cm102601v
129. Katz, M. J.; Brown, Z. J.; Colon, Y. J.; Siu, P. W.; Scheidt, K. A.; Snurr, R. Q.; Hupp, J. T.; Farha, O. K., A facile synthesis of UiO-66, UiO-67 and their derivatives. Chemical Communications 2013, 49 (82), 9449-9451. 10.1039/C3CC46105J
130. Crawford, D.; Casaban, J.; Haydon, R.; Giri, N.; McNally, T.; James, S. L., Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent. Chemical Science 2015, 6 (3), 1645-1649. 10.1039/C4SC03217A
131. Yu, C.; Bourrelly, S.; Martineau, C.; Saidi, F.; Bloch, E.; Lavrard, H.; Taulelle, F.; Horcajada, P.; Serre, C.; Llewellyn, P. L.; Magnier, E.; Devic, T., Functionalization of Zr-based MOFs with alkyl and perfluoroalkyl groups: the effect on the water sorption behavior. Dalton Transactions 2015, 44 (45), 19687-19692. 10.1039/C5DT02908B
132. Pachfule, P.; Chen, Y.; Jiang, J.; Banerjee, R., Fluorinated Metal–Organic Frameworks: Advantageous for Higher H2 and CO2 Adsorption or Not? Chemistry – A European Journal 2011, 18 (2), 688-694. 10.1002/chem.201102295
133. He, H.; Sun, Q.; Gao, W.; Perman Jason, A.; Sun, F.; Zhu, G.; Aguila, B.; Forrest, K.; Space, B.; Ma, S., A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation. Angewandte Chemie International Edition 2018, 0 (0). 10.1002/anie.201801122 121 134. Iremonger, S. S.; Liang, J.; Vaidhyanathan, R.; Martens, I.; Shimizu, G. K. H.; Daff, T. D.; Aghaji, M. Z.; Yeganegi, S.; Woo, T. K., Phosphonate Monoesters as Carboxylate-like Linkers for Metal Organic Frameworks. Journal of the American Chemical Society 2011, 133 (50), 20048- 20051. 10.1021/ja207606u
135. Taylor, J. M.; Vaidhyanathan, R.; Iremonger, S. S.; Shimizu, G. K. H., Enhancing Water Stability of Metal–Organic Frameworks via Phosphonate Monoester Linkers. Journal of the American Chemical Society 2012, 134 (35), 14338-14340. 10.1021/ja306812r
136. Gelfand, B. S.; Lin, J.-B.; Shimizu, G. K. H., Design of a Humidity-Stable Metal–Organic Framework Using a Phosphonate Monoester Ligand. Inorganic Chemistry 2015, 54 (4), 1185- 1187. 10.1021/ic502478u
137. Cotton Simon, A., Scandium, Yttrium & the Lanthanides: Inorganic & Coordination Chemistry. Encyclopedia of Inorganic Chemistry 2006. doi:10.1002/0470862106.ia211 10.1002/0470862106.ia211
138. Li, B.; Chen, B., Porous Lanthanide Metal–Organic Frameworks for Gas Storage and Separation. In Lanthanide Metal-Organic Frameworks, Cheng, P., Ed. Springer Berlin Heidelberg: Berlin, Heidelberg, 2015; pp 75-107.
139. Cui, P.-P.; Zhang, X.-D.; Zhao, Y.; Chen, K.; Wang, P.; Sun, W.-Y., Structure, topology and property of metal-organic frameworks with pyridine-3,5-bis(phenyl-4-carboxylate) and varied metal centers. Microporous and Mesoporous Materials 2015, 208 (Complete), 188-195. 10.1016/j.micromeso.2015.02.005
140. Cui, P.-P.; Zhang, X.-D.; Zhao, Y.; Fu, A.-Y.; Sun, W.-Y., Synthesis, structure and adsorption properties of lanthanide-organic frameworks with pyridine-3,5-bis(phenyl-4- carboxylate). Dalton Transactions 2016, 45 (6), 2591-2597. 10.1039/C5DT03091A
141. Moeller, T., Periodicity and the lanthanides and actinides. Journal of Chemical Education 1970, 47 (6), 417. 10.1021/ed047p417
142. Dhakshinamoorthy, A.; Asiri, A. M.; Garcia, H., Mixed-metal or mixed-linker metal organic frameworks as heterogeneous catalysts. Catalysis Science & Technology 2016, 6 (14), 5238-5261. 10.1039/C6CY00695G 122 143. Zhang, H.; Shan, X.; Ma, Z.; Zhou, L.; Zhang, M.; Lin, P.; Hu, S.; Ma, E.; Li, R.; Du, S., A highly luminescent chameleon: fine-tuned emission trajectory and controllable energy transfer. Journal of Materials Chemistry C 2014, 2 (8), 1367-1371. 10.1039/C3TC31624F
144. Yang, Q.-Y.; Pan, M.; Wei, S.-C.; Li, K.; Du, B.-B.; Su, C.-Y., Linear Dependence of Photoluminescence in Mixed Ln-MOFs for Color Tunability and Barcode Application. Inorganic Chemistry 2015, 54 (12), 5707-5716. 10.1021/acs.inorgchem.5b00271
145. Dunning, S. G.; Nuñez, A. J.; Moore, M. D.; Steiner, A.; Lynch, V. M.; Sessler, J. L.; Holliday, B. J.; Humphrey, S. M., A Sensor for Trace H2O Detection in D2O. Chem 2017, 2 (4), 579-589. https://doi.org/10.1016/j.chempr.2017.02.010
146. Weng, D.; Zheng, X.; Chen, X.; Li, L.; Jin, L., Synthesis, Upconversion Luminescence and Magnetic Properties of New Lanthanide–Organic Frameworks with (43)2(46,66,83) Topology. European Journal of Inorganic Chemistry 2007, 2007 (21), 3410-3415. 10.1002/ejic.200700140
147. Auzel, F., Upconversion and Anti-Stokes Processes with f and d Ions in Solids. Chemical Reviews 2004, 104 (1), 139-174. 10.1021/cr020357g
148. Mahata, P.; Ramya, K. V.; Natarajan, S., Synthesis, structure and optical properties of rare- earth benzene carboxylates. Dalton Transactions 2007, (36), 4017-4026. 10.1039/B706363F
149. Medishetty, R.; Zareba, J. K.; Mayer, D.; Samoc, M.; Fischer, R. A., Nonlinear optical properties, upconversion and lasing in metal-organic frameworks. Chemical Society Reviews 2017, 46 (16), 4976-5004. 10.1039/C7CS00162B
150. Pereira, C. F.; Figueira, F.; Mendes, R. F.; Rocha, J.; Hupp, J. T.; Farha, O. K.; Simões, M. M. Q.; Tomé, J. P. C.; Paz, F. A. A., Bifunctional Porphyrin-Based Nano-Metal–Organic Frameworks: Catalytic and Chemosensing Studies. Inorganic Chemistry 2018, 57 (7), 3855-3864. 10.1021/acs.inorgchem.7b03214
151. Xu, H.; Jin, R.; Wu, C.; Yang, Y.; Qian, G., Two-photon up-conversion fluorescence of a neodymium organic framework Nd (BTC). Guang pu xue yu guang pu fen xi= Guang pu 2008, 28 (8), 1734-1736.
152. Mahato, P.; Monguzzi, A.; Yanai, N.; Yamada, T.; Kimizuka, N., Fast and long-range triplet exciton diffusion in metal-organic frameworks for photon upconversion at ultralow excitation power. Nature Materials 2015, 14 (9), 924-930. 10.1038/nmat4366 123 153. Park, J.; Xu, M.; Li, F.; Zhou, H.-C., 3D Long-Range Triplet Migration in a Water-Stable Metal–Organic Framework for Upconversion-Based Ultralow-Power in Vivo Imaging. Journal of the American Chemical Society 2018. 10.1021/jacs.8b01613
154. Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T., Metal– organic framework materials as chemical sensors. Chemical reviews 2011, 112 (2), 1105-1125.
155. Gutierrez, M.; Sanchez, F.; Douhal, A., Spectral and dynamical properties of a Zr-based MOF. Physical Chemistry Chemical Physics 2016, 18 (7), 5112-5120. 10.1039/C5CP04436G
156. Yang, J.; Yue, Q.; Li, G.-D.; Cao, J.-J.; Li, G.-H.; Chen, J.-S., Structures, Photoluminescence, Up-Conversion, and Magnetism of 2D and 3D Rare-Earth Coordination Polymers with Multicarboxylate Linkages. Inorganic Chemistry 2006, 45 (7), 2857-2865. 10.1021/ic051557o
157. Chen, D.-H.; Lin, L.; Sheng, T.-L.; Wen, Y.-H.; Zhu, X.-Q.; Zhang, L.-T.; Hu, S.-M.; Fu, R.-B.; Wu, X.-T., Syntheses, structures, luminescence and magnetic properties of seven isomorphous metal-organic frameworks based on 2,7-bis(4-benzoic acid)-N-(4-benzoic acid)carbazole. New Journal of Chemistry 2018, 42 (4), 2830-2837. 10.1039/C7NJ04048B
158. Denton, A. R.; Ashcroft, N. W., Vegard’s law. Physical review A 1991, 43 (6), 3161.
159. Gandouzi, M.; Hedhili, F.; Rekik, N., A density functional theory investigation of the structural and optoelectronic properties of InP 1− x Bi x alloys. Computational Materials Science 2018, 149, 307-315.
160. Nahory, R.; Pollack, M.; Johnston Jr, W.; Barns, R., Band gap versus composition and demonstration of Vegard’s law for In1− x Ga x As y P1− y lattice matched to InP. Applied Physics Letters 1978, 33 (7), 659-661.
161. Alivisatos, A. P., Semiconductor Clusters, Nanocrystals, and Quantum Dots. Science 1996, 271 (5251), 933.
162. Van de Walle, C. G.; Neugebauer, J., First-principles calculations for defects and impurities: Applications to III-nitrides. Journal of Applied Physics 2004, 95 (8), 3851-3879. 10.1063/1.1682673 124 163. SMART, SAINT, SADABS, and SHELXTL, Bruker AXS, Inc.: Madison, WI, 2002.
164. Sheldrick, G. M. SADABS, University of Göttingen, Germany, 1995.
165. Sheldrick, G., SHELXT - Integrated space-group and crystal-structure determination. Acta Crystallographica Section A 2015, 71 (1), 3-8. doi:10.1107/S2053273314026370
166. Sheldrick, G., SHELXTL, v. 2008/4. Bruker Analytical X-ray: Madison, WI 2008, 65.
167. CCDC Mercury, Cambridge Crystallographic Data Centre: Cambridge, England, 2002.
168. Materals Studio Release Notes, Release 6.0; Accelrys Software Inc.: 2011.
169. Das, S. K.; Chatterjee, S.; Bhunia, S.; Mondal, A.; Mitra, P.; Kumari, V.; Pradhan, A.; Bhaumik, A., A new strongly paramagnetic cerium-containing microporous MOF for CO2 fixation under ambient conditions. Dalton Transactions 2017, 46 (40), 13783-13792. 10.1039/C7DT02040F
170. Zalkin, A.; Forrester, J. D.; Templeton, D. H., Crystal Structure of Cerium Magnesium Nitrate Hydrate. The Journal of Chemical Physics 1963, 39 (11), 2881-2891. 10.1063/1.1734120
171. Stromyer, M. L.; Lilly, C. P.; Dillner, A. J.; Knaust, J. M., Crystal structures of [Ln(NO3)3([mu]2-bpydo)2], where Ln = Ce, Pr or Nd, and bpydo = 4,4'-bipyridine N,N'-dioxide: layered coordination networks containing 44 grids. Acta Crystallographica Section E 2016, 72 (1), 25-30. doi:10.1107/S205698901502318X
172. Silverstein, R. M.; Webster, F. X.; Kiemle, D. J.; Bryce, D. L., Spectrometric identification of organic compounds. Eighth edition. ed.; p viii, 455 pages.
173. Crabtree, R. H., The organometallic chemistry of the transition metals. 4th ed.; John Wiley: Hoboken, N.J., 2005; p xiii, 546 p.
174. Clark Stewart, J.; Segall Matthew, D.; Pickard Chris, J.; Hasnip Phil, J.; Probert Matt, I. J.; Refson, K.; Payne Mike, C., First principles methods using CASTEP. In Zeitschrift für Kristallographie - Crystalline Materials, 2005; Vol. 220, p 567. 125 175. Milinski, N. R., P.; Ribar, B.; Djuric, S., Tetraaquatri(nitrato)cerium(III), Ce(H2O)4(NO3) 3. Crystal Structure Communications 1982, 11, 1241-1244.
176. Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M., The Chemistry and Applications of Metal-Organic Frameworks. Science 2013, 341 (6149).
177. Macrae, C. F.; Edgington, P. R.; McCabe, P.; Pidcock, E.; Shields, G. P.; Taylor, R.; Towler, M.; van de Streek, J., Mercury: visualization and analysis of crystal structures. Journal of Applied Crystallography 2006, 39 (3), 453-457. doi:10.1107/S002188980600731X
178. Aldebert, P.; Traverse, J., Etude par diffraction neutronique des structures de haute temperature de La2O3 et Nd2O3. Materials Research Bulletin 1979, 14 (3), 303-323.
179. Kaduk, J. A.; Golab, J. T., Structures of 2,6-disubstituted naphthalenes. Acta Crystallographica Section B 1999, 55 (1), 85-94. doi:10.1107/S0108768198008945
180. Li, J.-R.; Kuppler, R. J.; Zhou, H.-C., Selective gas adsorption and separation in metal- organic frameworks. Chemical Society Reviews 2009, 38 (5), 1477-1504. 10.1039/B802426J
181. Meek Scott, T.; Greathouse Jeffery, A.; Allendorf Mark, D., Metal‐Organic Frameworks: A Rapidly Growing Class of Versatile Nanoporous Materials. Advanced Materials 2010, 23 (2), 249-267. 10.1002/adma.201002854
182. Gardner, M.; Comber, S., Determination of trace concentrations of hexavalent chromium. Analyst 2002, 127 (1), 153-156. 10.1039/B109374F
183. Mädler, S.; Sun, F.; Tat, C.; Sudakova, N.; Drouin, P.; Tooley, R. J.; Reiner, E. J.; Switzer, T. A.; Dyer, R.; Kingston, H. M. S.; Pamuku, M.; Furdui, V. I., Trace-Level Analysis of Hexavalent Chromium in Lake Sediment Samples Using Ion Chromatography Tandem Mass Spectrometry. Journal of Environmental Protection 2016, Vol.07No.03, 13. 10.4236/jep.2016.73037
184. Chong, M. N.; Jin, B.; Chow, C. W. K.; Saint, C., Recent developments in photocatalytic water treatment technology: A review. Water Research 2010, 44 (10), 2997-3027. https://doi.org/10.1016/j.watres.2010.02.039 126 185. Munter, R., Advanced oxidation processes–current status and prospects. Proc. Estonian Acad. Sci. Chem 2001, 50 (2), 59-80.
186. Lee, S.-Y.; Park, S.-J., TiO2 photocatalyst for water treatment applications. Journal of Industrial and Engineering Chemistry 2013, 19 (6), 1761-1769. https://doi.org/10.1016/j.jiec.2013.07.012
187. Kumar, S. G.; Devi, L. G., Review on Modified TiO2 Photocatalysis under UV/Visible Light: Selected Results and Related Mechanisms on Interfacial Charge Carrier Transfer Dynamics. The Journal of Physical Chemistry A 2011, 115 (46), 13211-13241. 10.1021/jp204364a
188. Standard Tables for Reference Solar Spectral Irradiances: DirectNormal and Hemispherical on 37° Tilted Surface. West Conshohocken, PA, 2012.
189. Smith, R. C.; Baker, K. S., Optical properties of the clearest natural waters (200–800 nm). Appl. Opt. 1981, 20 (2), 177-184. 10.1364/AO.20.000177
190. Carp, O.; Huisman, C. L.; Reller, A., Photoinduced reactivity of titanium dioxide. Progress in Solid State Chemistry 2004, 32 (1), 33-177. https://doi.org/10.1016/j.progsolidstchem.2004.08.001
191. Sclafani, A.; Herrmann, J. M., Comparison of the Photoelectronic and Photocatalytic Activities of Various Anatase and Rutile Forms of Titania in Pure Liquid Organic Phases and in Aqueous Solutions. The Journal of Physical Chemistry 1996, 100 (32), 13655-13661. 10.1021/jp9533584
192. Sunding, M.; Hadidi, K.; Diplas, S.; Løvvik, O.; Norby, T.; Gunnæs, A., XPS characterisation of in situ treated lanthanum oxide and hydroxide using tailored charge referencing and peak fitting procedures. Journal of Electron Spectroscopy and Related Phenomena 2011, 184 (7), 399-409.
193. Wang, S.; Gao, Q.; Wang, J., Thermodynamic Analysis of Decomposition of Thiourea and Thiourea Oxides. The Journal of Physical Chemistry B 2005, 109 (36), 17281-17289. 10.1021/jp051620v
194. Chen, X.; Wang, X.; Wang, Z.; Yu, W.; Qian, Y., Direct sulfidization synthesis of high- quality binary sulfides (WS2, MoS2, and V5S8) from the respective oxides. Materials Chemistry and Physics 2004, 87 (2), 327-331. https://doi.org/10.1016/j.matchemphys.2004.05.027 127 195. Du, W.; Qian, X.; Ma, X.; Gong, Q.; Cao, H.; Yin, J., Shape‐Controlled Synthesis and Self‐Assembly of Hexagonal Covellite (CuS) Nanoplatelets. Chemistry-A European Journal 2007, 13 (11), 3241-3247.
196. Shi, W.; Huo, L.; Wang, H.; Zhang, H.; Yang, J.; Wei, P., Hydrothermal growth and gas sensing property of flower-shaped SnS2 nanostructures. Nanotechnology 2006, 17 (12), 2918.
197. Botta, M.; Castagnolo, D.; Pagano, M.; Bernardini, M., Domino alkylation-cyclization reaction of propargyl bromides with thioureas/thiopyrimidinones: a new facile synthesis of 2- aminothiazoles and 5H-thiazolo [3, 2-a] pyrimidin-5-ones. Synlett 2009, 2009 (13), 2093-2096.
198. Beall, G. W.; Milligan, W. O.; Wolcott, H. A., Structural trends in the lanthanide trihydroxides. Journal of Inorganic and Nuclear Chemistry 1977, 39 (1), 65-70. https://doi.org/10.1016/0022-1902(77)80434-X
199. O’Hare, P.; Curtiss, L., Thermochemistry of (germanium+ sulfur): IV. Critical evaluation of the thermodynamic properties of solid and gaseous germanium (II) sulfide GeS and germanium (IV) disulfide GeS2, and digermanium disulfide Ge2S2 (g). Enthalpies of dissociation of bonds in GeS (g), GeS2 (g), and Ge2S2 (g). The Journal of Chemical Thermodynamics 1995, 27 (6), 643- 662.
200. Reichle, W. T., The Reaction of Carbon Disulfide with Organotin Oxides and Related Substances. Inorganic Chemistry 1962, 1 (3), 650-653.
201. López, R.; Gómez, R., Band-gap energy estimation from diffuse reflectance measurements on sol–gel and commercial TiO2: a comparative study. Journal of Sol-Gel Science and Technology 2012, 61 (1), 1-7. 10.1007/s10971-011-2582-9
202. Gray, J. L.; Luque, A.; Hegedus, S., Handbook of photovoltaic science and engineering. Luque and S. Hegedus, Eds. West Sussex, England: John Wiley & Sons 2003, 14.
203. Quan, X.; Zhao, Q.; Tan, H.; Sang, X.; Wang, F.; Dai, Y., Comparative study of lanthanide oxide doped titanium dioxide photocatalysts prepared by coprecipitation and sol–gel process. Materials Chemistry and Physics 2009, 114 (1), 90-98.
128 204. Colombo, V.; Galli, S.; Choi, H. J.; Han, G. D.; Maspero, A.; Palmisano, G.; Masciocchi, N.; Long, J. R., High thermal and chemical stability in pyrazolate-bridged metal-organic frameworks with exposed metal sites. Chemical Science 2011, 2 (7), 1311-1319. 10.1039/C1SC00136A
205. Tomic, E. A., Thermal stability of coordination polymers. Journal of Applied Polymer Science 2003, 9 (11), 3745-3752. 10.1002/app.1965.070091121
206. Müller, P.; Bon, V.; Senkovska, I.; Getzschmann, J.; Weiss, M. S.; Kaskel, S., Crystal Engineering of Phenylenebis(azanetriyl))tetrabenzoate Based Metal–Organic Frameworks for Gas Storage Applications. Crystal Growth & Design 2017, 17 (6), 3221-3228. 10.1021/acs.cgd.7b00184
207. Ryan, K.; Lengyel, J.; Shatruk, M., Crystal Structure Prediction via Deep Learning. Journal of the American Chemical Society 2018. 10.1021/jacs.8b03913
208. Hendon, C. H.; Wittering, K. E.; Chen, T.-H.; Kaveevivitchai, W.; Popov, I.; Butler, K. T.; Wilson, C. C.; Cruickshank, D. L.; Miljanić, O. Š.; Walsh, A., Absorbate-Induced Piezochromism in a Porous Molecular Crystal. Nano Letters 2015, 15 (3), 2149-2154. 10.1021/acs.nanolett.5b00144
209. Witczak-Krempa, W.; Chen, G.; Kim, Y. B.; Balents, L., Correlated Quantum Phenomena in the Strong Spin-Orbit Regime. Annual Review of Condensed Matter Physics 2014, 5 (1), 57-82. 10.1146/annurev-conmatphys-020911-125138
210. Rota Martir, D.; Zysman-Colman, E., Supramolecular iridium(III) assemblies. Coordination Chemistry Reviews 2018, 364, 86-117. https://doi.org/10.1016/j.ccr.2018.03.016
211. Monna, F.; Lancelot, J.; Croudace, I. W.; Cundy, A. B.; Lewis, J. T., Pb Isotopic Composition of Airborne Particulate Material from France and the Southern United Kingdom: Implications for Pb Pollution Sources in Urban Areas. Environmental Science \& Technology 1997, 31 (8), 2277-2286. 10.1021/es960870+
212. Agamuthu, P.; Fauziah, S., Impacts of Municipal Solid Waste Management on Marine Pollution.
213. Batten Stuart, R.; Champness Neil, R.; Chen, X.-M.; Garcia-Martinez, J.; Kitagawa, S.; Öhrström, L.; O’Keeffe, M.; Paik Suh, M.; Reedijk, J., Terminology of metal–organic frameworks 129 and coordination polymers (IUPAC Recommendations 2013). In Pure and Applied Chemistry, 2013; Vol. 85, p 1715.
130
APPENDIX A
TABLES OF ATOMIC COORDINATES, BOND LENGTHS, AND ANGLES 131 Table A 1: Atomic coordinates and isotropic displacement parameters for
[Ce(NO3)(NDC)•2DMA]n.
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
4 4 4 x (10 ) y (10 ) z (10 ) U(eq) (Å2x 103) C(1) 10366(6) 823(4) 3880(4) 26(2) Ce(1) 8399(1) 140(1) 5026(1) 23(1) N(1) 6861(7) -584(6) 4090(5) 67(3) O(1) 9662(4) 575(3) 4232(3) 36(1) C(2) 10132(5) 1353(4) 3307(4) 26(2) N(2) 6483(7) 461(5) 6993(4) 69(3) O(2) 9032(4) -978(3) 4488(3) 39(1) C(3) 9218(5) 1736(4) 3301(4) 33(2) N(3) 6241(8) 1809(6) 5168(5) 69(3) O(3) 8740(4) -659(3) 6020(3) 40(1) C(4) 9056(5) 2262(5) 2812(4) 36(2) O(4) 7158(4) 377(3) 5943(3) 40(1) C(5) 9777(6) 2429(4) 2300(4) 28(2) O(6) 7612(4) 1315(3) 4736(3) 40(1) C(6) 9631(6) 2992(4) 1803(4) 32(2) O(5) 9355(4) 963(3) 5769(3) 34(1) O(8) 7400(7) -80(4) 3863(4) 75(2) C(9) 11257(6) 2760(4) 1316(4) 30(2) C(10) 11400(5) 2195(4) 1772(4) 29(2) O(7) 6881(5) -695(5) 4734(4) 65(2) C(11) 10678(5) 2024(4) 2279(3) 24(2) O(9) 6315(9) -937(8) 3716(6) 140(5) C(12) 10837(5) 1490(4) 2793(4) 28(2) C(8) 9785(6) -1209(4) 4173(4) 27(2) C(7) 9635(5) -1835(4) 3673(4) 27(2) C(14) 6196(14) -622(9) 6381(8) 126(7) C(15) 6659(7) 122(6) 6427(6) 53(2) C(16) 5832(12) 237(7) 7565(6) 89(5) C(17) 6992(15) 1184(8) 7077(8) 122(7) C(18) 7168(8) 1810(6) 5086(5) 56(3) C(19) 5663(8) 1210(7) 4826(7) 71(3) C(20) 5674(10) 2346(8) 5557(7) 91(4) C(21) 7744(10) 2430(6) 5401(7) 75(4)
132 Table A 2: Bond Lengths (Å) and Angles (°) for [Ce(NO3)(NDC)•2DMA]n
C(1)-O(1) 1.248(9) C(1)-O(3)#1 1.255(9) C(1)-C(2) 1.501(9) Ce(1)-O(1) 2.417(5) Ce(1)-O(5) 2.442(5) Ce(1)-O(3) 2.445(5) Ce(1)-O(2) 2.449(5) Ce(1)-O(4) 2.463(5) Ce(1)-O(6) 2.468(5) Ce(1)-O(7) 2.615(6) Ce(1)-O(8) 2.631(7) N(1)-O(9) 1.215(12) N(1)-O(7) 1.250(12) N(1)-O(8) 1.254(12) C(2)-C(12) 1.389(10) C(2)-C(3) 1.418(10) N(2)-C(15) 1.273(13) N(2)-C(16) 1.460(13) N(2)-C(17) 1.503(15) O(2)-C(8) 1.253(9) C(3)-C(4) 1.362(10) N(3)-C(18) 1.259(15) N(3)-C(20) 1.453(13) N(3)-C(19) 1.498(16) O(3)-C(1)#1 1.255(9) C(4)-C(5) 1.413(10) O(4)-C(15) 1.236(11) C(5)-C(6) 1.418(10) C(5)-C(11) 1.424(10) O(6)-C(18) 1.277(12) C(6)-C(7)#2 1.381(11) O(5)-C(8)#1 1.249(9) C(9)-C(10) 1.369(10) C(9)-C(7)#2 1.413(10) C(10)-C(11) 1.409(10) C(11)-C(12) 1.405(10) C(8)-O(5)#1 1.249(9) C(8)-C(7) 1.509(9) C(7)-C(6)#3 1.381(11) 133 C(7)-C(9)#3 1.413(10) C(14)-C(15) 1.504(16) C(18)-C(21) 1.504(15) O(1)-C(1)-O(3)#1 124.0(7) O(1)-C(1)-C(2) 118.1(7) O(3)#1-C(1)-C(2) 117.9(6) O(1)-Ce(1)-O(5) 77.88(19) O(1)-Ce(1)-O(3) 123.71(19) O(5)-Ce(1)-O(3) 79.59(19) O(1)-Ce(1)-O(2) 76.60(19) O(5)-Ce(1)-O(2) 125.45(18) O(3)-Ce(1)-O(2) 76.05(19) O(1)-Ce(1)-O(4) 150.10(19) O(5)-Ce(1)-O(4) 80.37(19) O(3)-Ce(1)-O(4) 71.31(19) O(2)-Ce(1)-O(4) 133.2(2) O(1)-Ce(1)-O(6) 82.63(18) O(5)-Ce(1)-O(6) 79.38(19) O(3)-Ce(1)-O(6) 141.26(19) O(2)-Ce(1)-O(6) 142.01(19) O(4)-Ce(1)-O(6) 73.35(19) O(1)-Ce(1)-O(7) 127.6(2) O(5)-Ce(1)-O(7) 154.0(2) O(3)-Ce(1)-O(7) 87.8(2) O(2)-Ce(1)-O(7) 72.1(2) O(4)-Ce(1)-O(7) 74.0(2) O(6)-Ce(1)-O(7) 97.4(2) O(1)-Ce(1)-O(8) 83.1(3) O(5)-Ce(1)-O(8) 148.9(2) O(3)-Ce(1)-O(8) 131.5(2) O(2)-Ce(1)-O(8) 72.2(2) O(4)-Ce(1)-O(8) 106.4(3) O(6)-Ce(1)-O(8) 74.0(2) O(7)-Ce(1)-O(8) 47.9(3) O(9)-N(1)-O(7) 120.5(12) O(9)-N(1)-O(8) 122.7(12) O(7)-N(1)-O(8) 116.7(8) C(1)-O(1)-Ce(1) 173.7(5) C(12)-C(2)-C(3) 119.9(6) C(12)-C(2)-C(1) 119.4(6) C(3)-C(2)-C(1) 120.6(6) 134 C(15)-N(2)-C(16) 127.7(10) C(15)-N(2)-C(17) 116.0(9) C(16)-N(2)-C(17) 116.4(9) C(8)-O(2)-Ce(1) 140.1(5) C(4)-C(3)-C(2) 119.7(7) C(18)-N(3)-C(20) 125.7(12) C(18)-N(3)-C(19) 117.6(10) C(20)-N(3)-C(19) 116.7(11) C(1)#1-O(3)-Ce(1) 116.2(5) C(3)-C(4)-C(5) 121.4(7) C(15)-O(4)-Ce(1) 146.6(6) C(4)-C(5)-C(6) 121.9(7) C(4)-C(5)-C(11) 119.4(6) C(6)-C(5)-C(11) 118.7(7) C(18)-O(6)-Ce(1) 134.9(5) C(7)#2-C(6)-C(5) 120.8(7) C(8)#1-O(5)-Ce(1) 139.9(5) N(1)-O(8)-Ce(1) 96.7(6) C(10)-C(9)-C(7)#2 120.7(7) C(9)-C(10)-C(11) 120.7(7) N(1)-O(7)-Ce(1) 97.5(6) C(12)-C(11)-C(10) 122.2(7) C(12)-C(11)-C(5) 118.4(6) C(10)-C(11)-C(5) 119.4(6) C(2)-C(12)-C(11) 121.2(7) O(5)#1-C(8)-O(2) 125.9(6) O(5)#1-C(8)-C(7) 117.1(6) O(2)-C(8)-C(7) 117.0(7) C(6)#3-C(7)-C(9)#3 119.7(6) C(6)#3-C(7)-C(8) 119.9(7) C(9)#3-C(7)-C(8) 120.4(6) O(4)-C(15)-N(2) 123.6(10) O(4)-C(15)-C(14) 121.8(10) N(2)-C(15)-C(14) 114.7(10) N(3)-C(18)-O(6) 121.9(11) N(3)-C(18)-C(21) 117.6(11) O(6)-C(18)-C(21) 120.5(10) Symmetry transformations used to generate equivalent atoms: #1 -x+2,-y,-z+1 #2 -x+2,y+1/2,-z+1/2 #3 -x+2,y-1/2,-z+1/2
135 Table A 3: Anisotropic displacement parameters for [Ce(NO3)(NDC)•2DMA]n
The anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ...
+ 2 h k a* b* U12 ] where U has units of (Å2x 103).
11 22 33 23 13 12 U U U U U U C(1) 35(4) 19(3) 25(3) 2(3) 0(3) 2(3) Ce(1) 23(1) 24(1) 21(1) 0(1) 1(1) 2(1) N(1) 55(5) 76(7) 70(6) -28(5) -15(5) -6(5) O(1) 49(3) 27(3) 30(3) 7(2) 8(3) -2(2) C(2) 25(4) 24(3) 28(4) 5(3) -3(3) -6(3) N(2) 90(7) 72(6) 47(5) 0(4) 30(5) -10(5) O(2) 43(3) 31(3) 41(3) -15(2) -4(3) 6(2) C(3) 24(4) 37(4) 37(4) 14(3) 5(3) -2(3) N(3) 71(7) 77(7) 60(5) 8(5) 11(5) 36(5) O(3) 39(3) 41(3) 40(3) 15(3) 1(3) 4(3) C(4) 14(4) 43(5) 50(5) 19(4) 7(3) 5(3) O(4) 36(3) 49(3) 35(3) 3(3) 14(3) 2(3) C(5) 29(4) 29(4) 27(4) 6(3) 0(3) -2(3) O(6) 39(3) 37(3) 42(3) 9(3) 6(3) 19(3) C(6) 23(4) 30(4) 44(4) 12(3) -4(3) 3(3) O(5) 32(3) 31(3) 38(3) -12(2) -4(2) 1(2) O(8) 97(6) 67(5) 60(5) 4(4) -36(5) -3(5) C(9) 27(4) 37(4) 26(4) 6(3) 6(3) -3(3) C(10) 18(3) 37(4) 33(4) 6(3) 2(3) 2(3) O(7) 35(4) 95(6) 66(5) -26(4) 9(3) -25(4) C(11) 23(4) 26(4) 24(3) 0(3) -3(3) -6(3) O(9) 120(9) 193(13) 108(8) -57(8) -39(7) -76(9) C(12) 25(4) 29(4) 28(4) 5(3) 1(3) 1(3) C(8) 35(4) 19(3) 27(4) -5(3) -2(3) 6(3) C(7) 24(4) 29(4) 29(4) -6(3) -4(3) 6(3) C(14) 176(17) 111(12) 90(10) -51(9) 47(11) -95(12) C(15) 42(5) 62(6) 55(6) 6(5) 4(5) 12(5) C(16) 141(13) 69(7) 59(7) -11(6) 51(8) -38(8) C(17) 198(18) 84(10) 83(10) -26(8) 59(11) -76(11) C(18) 56(6) 61(7) 51(6) 23(5) 1(5) 10(5) C(19) 44(6) 65(7) 105(9) 13(7) -8(6) -5(5) C(20) 92(9) 100(10) 82(9) -13(8) 13(7) 63(8) C(21) 92(9) 43(6) 90(9) -4(6) -36(7) 1(6) 136 ______
Table A 4: Hydrogen coordinates and isotropic displacement parameters for
[Ce(NO3)(NDC)•2DMA]n
4 4 4 2 3 x (10 ) y (10 ) z (10 ) U(eq) (Å x 10 ) H(3) 8726 1628 3634 39 H(4) 8453 2518 2815 43 H(6) 9029 3250 1798 39 H(9) 11756 2879 993 36 H(10) 11987 1919 1747 35 H(11) 11431 1221 2790 33 H(14A) 6397 -854 5948 189 H(14B) 5478 -576 6391 189 H(14C) 6413 -915 6774 189 H(23A) 5340 -103 7390 134 H(23B) 5500 661 7756 134 H(23C) 6223 4 7927 134 H(16A) 7274 1332 6632 183 H(16B) 7517 1142 7422 183 H(16C) 6514 1546 7230 183 H(19B) 5136 1419 4544 107 H(19C) 5376 898 5182 107 H(19A) 6101 926 4531 107 H(20A) 5336 2110 5943 137 H(20B) 5189 2571 5251 137 H(20C) 6120 2716 5737 137 H(21A) 8397 2454 5188 113 H(21B) 7813 2353 5900 113 H(21C) 7394 2884 5319 113
137 Table A 5: Atomic coordinates and isotropic displacement parameters for
[Nd(NO3)(NDC)•2DMA]n
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
x (104) y (104) z (104) U(eq) (Å2 x 103) C(1) 10296(3) 837(2) 3893(2) 34(1) N(1) 6458(5) 416(3) 6973(3) 90(2) Nd(1) 8408(1) 118(1) 5032(1) 28(1) O(1) 9586(2) 590(2) 4241(2) 43(1) C(2) 10086(3) 1380(2) 3321(2) 31(1) N(2) 6250(6) 1784(4) 5165(3) 106(2) O(2) 11181(2) 672(2) 3998(2) 45(1) C(3) 9189(3) 1764(3) 3316(2) 42(1) N(3) 6911(4) -614(3) 4113(3) 79(2) O(3) 9325(2) 937(2) 5773(2) 43(1) C(4) 9032(3) 2294(3) 2830(3) 46(1) O(4) 7207(2) 319(2) 5955(2) 50(1) C(5) 9743(3) 2459(2) 2312(2) 35(1) C(6) 9607(3) 3020(2) 1811(2) 38(1) C(7) 10324(3) 3188(2) 1336(2) 34(1) O(7) 7581(3) 1250(2) 4748(2) 51(1) C(8) 11208(3) 2787(2) 1330(2) 39(1) O(8) 10926(2) 962(2) 5512(2) 44(1) C(9) 11349(3) 2226(2) 1788(2) 38(1) C(10) 10632(3) 2056(2) 2300(2) 32(1) O(10) 7443(4) -114(3) 3876(2) 82(1) C(11) 10787(3) 1517(2) 2820(2) 34(1) O(11) 6956(3) -728(3) 4755(2) 77(1) C(12) 10175(3) 1185(2) 5830(2) 34(1) O(12) 6377(5) -971(4) 3733(3) 152(3) C(14) 6709(4) 78(4) 6441(3) 66(2) C(15) 6305(9) -700(5) 6410(5) 157(5) C(16) 6914(9) 1169(5) 7048(5) 166(5) 138 C(17) 5819(7) 200(4) 7550(4) 114(3) C(20) 7122(6) 1746(4) 5074(3) 86(2) C(21) 7713(6) 2396(3) 5384(4) 103(3) C(22) 5674(5) 1137(5) 4813(5) 102(3) C(23) 5677(7) 2331(5) 5529(4) 127(4)
Table A 6: Bond lengths [Å] and angles [°] for [Nd(NO3)(NDC)•2DMA]n
C(1)-O(2) 1.255(5) C(1)-O(1) 1.256(5) C(1)-C(2) 1.505(5) N(1)-C(14) 1.235(7) N(1)-C(17) 1.456(7) N(1)-C(16) 1.522(9) Nd(1)-O(1) 2.361(3) Nd(1)-O(3) 2.410(3) Nd(1)-O(2)#1 2.414(3) Nd(1)-O(8)#1 2.414(3) Nd(1)-O(7) 2.424(3) Nd(1)-O(4) 2.425(3) Nd(1)-O(11) 2.566(4) Nd(1)-O(10) 2.597(4) Nd(1)-N(3) 3.001(5) C(2)-C(11) 1.371(6) C(2)-C(3) 1.408(6) N(2)-C(20) 1.199(9) N(2)-C(23) 1.448(8) N(2)-C(22) 1.573(10) O(2)-Nd(1)#1 2.414(3) C(3)-C(4) 1.360(6) N(3)-O(12) 1.215(6) N(3)-O(11) 1.242(7) N(3)-O(10) 1.252(7) 139 O(3)-C(12) 1.247(5) C(4)-C(5) 1.414(6) O(4)-C(14) 1.230(6) C(5)-C(6) 1.415(6) C(5)-C(10) 1.417(6) C(6)-C(7) 1.365(6) C(7)-C(8) 1.409(6) C(7)-C(12)#2 1.514(5) O(7)-C(20) 1.267(7) C(8)-C(9) 1.363(6) O(8)-C(12) 1.254(5) O(8)-Nd(1)#1 2.415(3) C(9)-C(10) 1.413(6) C(10)-C(11) 1.415(5) C(12)-C(7)#3 1.514(5) C(14)-C(15) 1.532(9) C(20)-C(21) 1.556(10) O(2)-C(1)-O(1) 124.3(4) O(2)-C(1)-C(2) 117.3(4) O(1)-C(1)-C(2) 118.4(4) C(14)-N(1)-C(17) 130.2(7) C(14)-N(1)-C(16) 114.9(6) C(17)-N(1)-C(16) 114.8(6) O(1)-Nd(1)-O(3) 78.11(11) O(1)-Nd(1)-O(2)#1 123.49(11) O(3)-Nd(1)-O(2)#1 78.95(11) O(1)-Nd(1)-O(8)#1 77.00(11) O(3)-Nd(1)-O(8)#1 124.82(11) O(2)#1-Nd(1)-O(8)#1 75.34(11) O(1)-Nd(1)-O(7) 81.77(11) O(3)-Nd(1)-O(7) 80.45(12) O(2)#1-Nd(1)-O(7) 142.49(11) O(8)#1-Nd(1)-O(7) 141.56(11) O(1)-Nd(1)-O(4) 149.46(11) 140 O(3)-Nd(1)-O(4) 80.12(11) O(2)#1-Nd(1)-O(4) 72.13(11) O(8)#1-Nd(1)-O(4) 133.43(11) O(7)-Nd(1)-O(4) 73.69(11) O(1)-Nd(1)-O(11) 127.74(13) O(3)-Nd(1)-O(11) 153.61(12) O(2)#1-Nd(1)-O(11) 88.34(14) O(8)#1-Nd(1)-O(11) 72.68(13) O(7)-Nd(1)-O(11) 96.73(14) O(4)-Nd(1)-O(11) 73.97(13) O(1)-Nd(1)-O(10) 82.08(15) O(3)-Nd(1)-O(10) 149.26(13) O(2)#1-Nd(1)-O(10) 131.79(14) O(8)#1-Nd(1)-O(10) 72.02(13) O(7)-Nd(1)-O(10) 73.60(14) O(4)-Nd(1)-O(10) 107.39(15) O(11)-Nd(1)-O(10) 48.56(15) O(1)-Nd(1)-N(3) 104.59(15) O(3)-Nd(1)-N(3) 166.26(14) O(2)#1-Nd(1)-N(3) 109.47(16) O(8)#1-Nd(1)-N(3) 68.63(13) O(7)-Nd(1)-N(3) 86.57(15) O(4)-Nd(1)-N(3) 91.98(15) O(11)-Nd(1)-N(3) 24.19(15) O(10)-Nd(1)-N(3) 24.51(15) C(1)-O(1)-Nd(1) 171.8(3) C(11)-C(2)-C(3) 120.3(4) C(11)-C(2)-C(1) 119.6(4) C(3)-C(2)-C(1) 120.1(4) C(20)-N(2)-C(23) 129.9(9) C(20)-N(2)-C(22) 112.7(7) C(23)-N(2)-C(22) 117.4(7) C(1)-O(2)-Nd(1)#1 119.3(3) C(4)-C(3)-C(2) 119.9(4) 141 O(12)-N(3)-O(11) 121.6(7) O(12)-N(3)-O(10) 121.8(7) O(11)-N(3)-O(10) 116.7(5) O(12)-N(3)-Nd(1) 173.0(6) O(11)-N(3)-Nd(1) 57.8(3) O(10)-N(3)-Nd(1) 59.3(3) C(12)-O(3)-Nd(1) 139.3(3) C(3)-C(4)-C(5) 121.4(4) C(14)-O(4)-Nd(1) 149.4(4) C(4)-C(5)-C(6) 122.5(4) C(4)-C(5)-C(10) 118.8(4) C(6)-C(5)-C(10) 118.8(4) C(7)-C(6)-C(5) 121.2(4) C(6)-C(7)-C(8) 119.6(4) C(6)-C(7)-C(12)#2 120.0(4) C(8)-C(7)-C(12)#2 120.4(4) C(20)-O(7)-Nd(1) 137.5(3) C(9)-C(8)-C(7) 120.7(4) C(12)-O(8)-Nd(1)#1 141.2(3) C(8)-C(9)-C(10) 120.8(4) C(9)-C(10)-C(11) 122.4(4) C(9)-C(10)-C(5) 118.8(4) C(11)-C(10)-C(5) 118.7(4) N(3)-O(10)-Nd(1) 96.2(3) C(2)-C(11)-C(10) 120.8(4) N(3)-O(11)-Nd(1) 98.0(4) O(3)-C(12)-O(8) 126.3(4) O(3)-C(12)-C(7)#3 117.2(4) O(8)-C(12)-C(7)#3 116.6(4) O(4)-C(14)-N(1) 126.0(7) O(4)-C(14)-C(15) 120.2(6) N(1)-C(14)-C(15) 113.7(6) N(2)-C(20)-O(7) 126.8(9) N(2)-C(20)-C(21) 114.2(8) 142 O(7)-C(20)-C(21) 118.9(7) Symmetry transformations used to generate equivalent atoms: #1 -x+2,-y,-z+1 #2 x,-y+1/2,z-1/2 #3 x,-y+1/2,z+1/2
Table A 7: Anisotropic displacement parameters for [Nd(NO3)(NDC)•2DMA]n
The anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ...
+ 2 h k a* b* U12 ] where U has units of (Å2x 103)
33 23 13 12 U11 U22 U U U U C(1) 50(3) 27(2) 26(2) 2(2) 1(2) 2(2) N(1) 125(5) 88(4) 57(3) 4(3) 43(3) 3(4) Nd(1) 32(1) 28(1) 23(1) 0(1) 1(1) 2(1) O(1) 57(2) 38(2) 34(2) 9(1) 12(2) -7(2) C(2) 33(2) 31(2) 28(2) 6(2) -1(2) -5(2) N(2) 121(6) 120(5) 76(4) 21(4) 23(4) 80(5) O(2) 52(2) 49(2) 35(2) 18(1) 1(2) 10(2) C(3) 33(2) 55(3) 39(2) 16(2) 9(2) -3(2) N(3) 62(3) 91(4) 85(4) -32(3) -23(3) -8(3) O(3) 47(2) 38(2) 44(2) -16(1) -2(2) -3(2) C(4) 30(2) 55(3) 53(3) 22(2) 9(2) 7(2) O(4) 47(2) 60(2) 42(2) 4(2) 20(2) 5(2) C(5) 32(2) 40(2) 33(2) 10(2) -1(2) -1(2) C(6) 31(2) 44(3) 40(2) 17(2) 1(2) 5(2) C(7) 38(2) 30(2) 33(2) 10(2) -4(2) -4(2) O(7) 55(2) 48(2) 49(2) 9(2) 6(2) 22(2) C(8) 39(2) 44(3) 35(2) 10(2) 7(2) -4(2) O(8) 47(2) 39(2) 44(2) -16(1) 5(2) 7(2) C(9) 35(2) 42(2) 37(2) 12(2) 5(2) 4(2) C(10) 32(2) 34(2) 31(2) 6(2) 0(2) -4(2) O(10) 101(4) 79(3) 67(3) 0(2) -37(3) -5(3) C(11) 34(2) 35(2) 33(2) 7(2) -1(2) 1(2) 143 O(11) 58(2) 100(3) 73(3) -26(3) 8(2) -27(2) C(12) 44(3) 29(2) 30(2) -4(2) -2(2) 6(2) O(12) 132(5) 198(7) 125(5) -63(5) -40(4) -72(5) C(14) 59(4) 87(4) 53(3) 8(3) 12(3) 11(3) C(15) 248(13) 118(7) 106(7) -45(6) 67(8) -111(8) C(16) 288(15) 97(6) 112(7) -36(5) 85(8) -100(8) C(17) 168(9) 100(5) 75(5) -10(4) 73(5) -40(6) C(20) 94(5) 110(6) 56(4) 40(4) 15(4) 52(5) C(21) 153(8) 45(4) 111(6) -6(4) -52(6) 4(4) C(22) 64(4) 105(6) 137(7) 9(6) -11(5) -4(4) C(23) 148(8) 131(7) 102(6) -4(5) 32(6) 95(6)
Table A 8: Hydrogen coordinates and isotropic displacement parameters for
[Nd(NO3)(NDC)•2DMA]n
x (104) y (104) z (104) U(eq) (Å2x 103) H(3) 8704 1656 3645 51 H(4) 8444 2553 2838 55 H(6) 9018 3277 1806 46 H(8) 11700 2905 1010 47 H(9) 11924 1952 1763 46 H(11) 11371 1253 2821 41 H(15A) 6450 -947 6842 236 H(15B) 6607 -956 6026 236 H(15C) 5605 -685 6341 236 H(16A) 7134 1336 6597 248 H(16B) 7463 1145 7364 248 H(16C) 6431 1501 7230 248 H(17A) 5366 -166 7390 171 H(17B) 5459 615 7715 171 H(17C) 6211 6 7926 171 H(21A) 7405 2845 5250 155 144 H(21B) 8375 2385 5207 155 H(21C) 7725 2359 5887 155 H(22A) 6080 915 4461 153 H(22B) 5083 1319 4600 153 H(22C) 5507 783 5164 153 H(23A) 5214 2546 5209 190 H(23B) 6108 2702 5708 190 H(23C) 5328 2109 5911 190
Table A 9: Atomic coordinates and isotropic displacement parameters for
[Eu(NO3(NDC)•2DMA]n
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
x (104) y (104) z (104) U(eq) (104 x Å2) C(1) 9265(2) 8459(2) 7156(2) 30(1) C(2) 9956(2) 8595(2) 6656(2) 27(1) C(3) 10854(2) 8202(2) 6660(2) 34(1) C(4) 11009(2) 7669(2) 7144(2) 38(1) C(4A) 10292(2) 7509(2) 7675(2) 30(1) C(5) 10425(2) 6954(2) 8176(2) 34(1) C(6) 9717(2) 6790(2) 8657(2) 29(1) C(7) 8824(2) 7202(2) 8664(2) 34(1) C(8) 8694(2) 7762(2) 8202(2) 35(1) C(8A) 9408(2) 7924(2) 7682(2) 27(1) C(9) 9751(2) 9140(2) 6087(2) 29(1) O(1) 9523(2) 10609(1) 4255(1) 38(1) O(2) 8881(2) 9313(1) 5977(1) 39(1) Eu(1) 8415(1) 10098(1) 5036(1) 21(1) O(3) 10897(2) 10948(1) 5512(1) 39(1) O(4) 9299(2) 10912(1) 5770(1) 37(1) C(10) 10146(2) 11163(2) 5834(2) 29(1) O(5) 7476(3) 9866(2) 3883(2) 72(1) 145 O(6) 7005(2) 9245(2) 4771(2) 68(1) N(1) 6953(3) 9369(3) 4115(2) 72(1) O(7) 6419(3) 9019(4) 3739(3) 139(2) O(80) 7244(2) 10277(2) 5958(1) 44(1) C(80) 6744(3) 10018(2) 6439(3) 53(1) C(81) 6476(4) 9210(4) 6441(4) 94(2) N(80) 6441(3) 10396(2) 6961(2) 74(1) C(82) 5814(6) 10161(3) 7542(3) 111(3) C(83) 6767(6) 11165(3) 7010(4) 151(4) O(90) 7553(2) 11198(2) 4764(2) 47(1) C(90) 7055(5) 11690(5) 5071(2) 84(2) C(91) 7642(5) 12375(3) 5373(4) 94(2) N(90) 6220(5) 11739(4) 5144(2) 106(2) C(92) 5652(4) 11069(5) 4803(4) 104(2) C(93) 5583(5) 12269(4) 5481(4) 121(2)
Table A 10: Bond lengths [Å] and angles [°] for [Eu(NO3)(NDC)•2DMA]n
C(1)-C(2) 1.362(4) C(1)-C(8A) 1.414(4) C(2)-C(3) 1.418(4) C(2)-C(9) 1.497(4) C(3)-C(4) 1.358(4) C(4)-C(4A) 1.435(4) C(4A)-C(5) 1.405(4) C(4A)-C(8A) 1.423(4) C(5)-C(6) 1.363(4) C(6)-C(7) 1.431(4) C(6)-C(10)#1 1.510(4) C(7)-C(8) 1.360(4) C(8)-C(8A) 1.417(4) C(9)-O(2) 1.243(4) C(9)-O(1)#2 1.269(4) C(9)-Eu(1) 3.220(3) 146 O(1)-C(9)#2 1.269(4) O(1)-Eu(1) 2.315(2) O(2)-Eu(1) 2.381(2) Eu(1)-O(4) 2.370(2) Eu(1)-O(3)#2 2.370(2) Eu(1)-O(90) 2.383(3) Eu(1)-O(80) 2.394(2) Eu(1)-O(6) 2.522(3) Eu(1)-O(5) 2.574(3) Eu(1)-N(1) 2.968(4) Eu(1)-Eu(1)#2 4.3336(4) O(3)-C(10) 1.255(4) O(3)-Eu(1)#2 2.370(2) O(4)-C(10) 1.248(4) C(10)-C(6)#3 1.510(4) O(5)-N(1) 1.235(5) O(6)-N(1) 1.271(5) N(1)-O(7) 1.204(5) O(80)-C(80) 1.235(5) C(80)-N(80) 1.279(6) C(80)-C(81) 1.521(8) N(80)-C(82) 1.461(6) N(80)-C(83) 1.476(7) O(90)-C(90) 1.269(8) C(90)-N(90) 1.149(8) C(90)-C(91) 1.592(10) N(90)-C(93) 1.450(6) N(90)-C(92) 1.587(10) C(2)-C(1)-C(8A) 121.9(3) C(1)-C(2)-C(3) 119.9(3) C(1)-C(2)-C(9) 119.9(3) C(3)-C(2)-C(9) 120.1(3) C(4)-C(3)-C(2) 120.2(3) C(3)-C(4)-C(4A) 121.2(3) 147 C(5)-C(4A)-C(8A) 119.1(3) C(5)-C(4A)-C(4) 122.5(3) C(8A)-C(4A)-C(4) 118.4(3) C(6)-C(5)-C(4A) 121.6(3) C(5)-C(6)-C(7) 119.4(3) C(5)-C(6)-C(10)#1 120.7(3) C(7)-C(6)-C(10)#1 119.9(3) C(8)-C(7)-C(6) 120.0(3) C(7)-C(8)-C(8A) 121.3(3) C(1)-C(8A)-C(8) 123.0(3) C(1)-C(8A)-C(4A) 118.5(3) C(8)-C(8A)-C(4A) 118.5(3) O(2)-C(9)-O(1)#2 124.4(3) O(2)-C(9)-C(2) 117.9(3) O(1)#2-C(9)-C(2) 117.7(3) O(2)-C(9)-Eu(1) 38.72(14) O(1)#2-C(9)-Eu(1) 85.75(18) C(2)-C(9)-Eu(1) 156.3(2) C(9)#2-O(1)-Eu(1) 169.3(2) C(9)-O(2)-Eu(1) 122.20(19) O(1)-Eu(1)-O(4) 78.19(9) O(1)-Eu(1)-O(3)#2 77.57(8) O(4)-Eu(1)-O(3)#2 124.37(8) O(1)-Eu(1)-O(2) 123.53(8) O(4)-Eu(1)-O(2) 78.33(9) O(3)#2-Eu(1)-O(2) 74.94(7) O(1)-Eu(1)-O(90) 80.89(9) O(4)-Eu(1)-O(90) 81.34(9) O(3)#2-Eu(1)-O(90) 141.17(9) O(2)-Eu(1)-O(90) 143.33(9) O(1)-Eu(1)-O(80) 148.21(9) O(4)-Eu(1)-O(80) 79.58(9) O(3)#2-Eu(1)-O(80) 134.12(9) O(2)-Eu(1)-O(80) 73.00(8) 148 O(90)-Eu(1)-O(80) 73.51(9) O(1)-Eu(1)-O(6) 128.07(10) O(4)-Eu(1)-O(6) 153.07(10) O(3)#2-Eu(1)-O(6) 73.46(10) O(2)-Eu(1)-O(6) 88.94(11) O(90)-Eu(1)-O(6) 95.89(11) O(80)-Eu(1)-O(6) 74.00(10) O(1)-Eu(1)-O(5) 80.94(11) O(4)-Eu(1)-O(5) 149.16(10) O(3)#2-Eu(1)-O(5) 71.87(10) O(2)-Eu(1)-O(5) 132.44(10) O(90)-Eu(1)-O(5) 73.10(11) O(80)-Eu(1)-O(5) 108.50(12) O(6)-Eu(1)-O(5) 49.50(12) O(1)-Eu(1)-N(1) 103.81(11) O(4)-Eu(1)-N(1) 166.12(10) O(3)#2-Eu(1)-N(1) 69.13(10) O(2)-Eu(1)-N(1) 110.69(12) O(90)-Eu(1)-N(1) 85.40(12) O(80)-Eu(1)-N(1) 92.76(11) O(6)-Eu(1)-N(1) 25.14(11) O(5)-Eu(1)-N(1) 24.46(12) O(1)-Eu(1)-C(9) 104.46(8) O(4)-Eu(1)-C(9) 71.75(8) O(3)#2-Eu(1)-C(9) 67.16(8) O(2)-Eu(1)-C(9) 19.07(7) O(90)-Eu(1)-C(9) 150.54(9) O(80)-Eu(1)-C(9) 89.70(8) O(6)-Eu(1)-C(9) 102.63(11) O(5)-Eu(1)-C(9) 136.11(10) N(1)-Eu(1)-C(9) 120.15(11) O(1)-Eu(1)-Eu(1)#2 50.48(6) O(4)-Eu(1)-Eu(1)#2 64.17(6) O(3)#2-Eu(1)-Eu(1)#2 61.69(5) 149 O(2)-Eu(1)-Eu(1)#2 73.05(6) O(90)-Eu(1)-Eu(1)#2 123.57(7) O(80)-Eu(1)-Eu(1)#2 134.22(7) O(6)-Eu(1)-Eu(1)#2 134.50(8) O(5)-Eu(1)-Eu(1)#2 117.02(9) N(1)-Eu(1)-Eu(1)#2 127.78(8) C(9)-Eu(1)-Eu(1)#2 53.98(6) C(10)-O(3)-Eu(1)#2 142.1(2) C(10)-O(4)-Eu(1) 139.3(2) O(4)-C(10)-O(3) 126.2(3) O(4)-C(10)-C(6)#3 117.1(3) O(3)-C(10)-C(6)#3 116.7(3) N(1)-O(5)-Eu(1) 95.9(3) N(1)-O(6)-Eu(1) 97.4(3) O(7)-N(1)-O(5) 121.8(5) O(7)-N(1)-O(6) 121.6(5) O(5)-N(1)-O(6) 116.7(4) O(7)-N(1)-Eu(1) 173.8(4) O(5)-N(1)-Eu(1) 59.6(2) O(6)-N(1)-Eu(1) 57.4(2) C(80)-O(80)-Eu(1) 149.1(3) O(80)-C(80)-N(80) 123.2(4) O(80)-C(80)-C(81) 120.4(5) N(80)-C(80)-C(81) 116.4(4) C(80)-N(80)-C(82) 128.1(5) C(80)-N(80)-C(83) 117.8(4) C(82)-N(80)-C(83) 114.1(4) C(90)-O(90)-Eu(1) 139.5(3) N(90)-C(90)-O(90) 129.8(8) N(90)-C(90)-C(91) 113.1(7) O(90)-C(90)-C(91) 117.0(5) C(90)-N(90)-C(93) 134.2(8) C(90)-N(90)-C(92) 111.9(6) C(93)-N(90)-C(92) 113.9(6) 150 Symmetry transformations used to generate equivalent atoms: #1 -x+2,y-1/2,-z+3/2 #2 -x+2,-y+2,-z+1 #3 -x+2,y+1/2,-z+3/2
Table A 11: Anisotropic displacement parameters for [Eu(NO3)(NDC)•2DMA]n
The anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ...
+ 2 h k a* b* U12 ] where U has units of (Å2x 103).
U11 U22 U33 U23 U13 U12 C(1) 32(2) 32(2) 25(2) 9(1) -1(1) 4(1) C(2) 36(2) 24(2) 21(2) 7(1) -2(1) -4(1) C(3) 32(2) 40(2) 31(2) 12(1) 9(1) -1(1) C(4) 30(2) 45(2) 38(2) 17(2) 6(1) 4(1) C(4A) 24(1) 35(2) 31(2) 11(1) -1(1) -2(1) C(5) 31(2) 36(2) 35(2) 14(2) -1(1) 3(1) C(6) 34(2) 29(2) 24(2) 9(1) -3(1) -5(1) C(7) 37(2) 37(2) 27(2) 12(1) 10(1) 1(2) C(8) 30(2) 41(2) 35(2) 12(2) 4(1) 4(1) C(8A) 27(1) 30(2) 25(2) 9(1) 0(1) -2(1) C(9) 43(2) 24(2) 19(2) 4(1) -1(1) -3(1) O(1) 53(1) 35(1) 26(1) 9(1) 13(1) -6(1) O(2) 46(1) 42(1) 28(1) 16(1) 2(1) 7(1) Eu(1) 26(1) 21(1) 16(1) 0(1) 1(1) 1(1) O(3) 46(1) 34(1) 38(1) -14(1) 5(1) 6(1) O(4) 42(1) 35(1) 34(1) -13(1) -3(1) -3(1) C(10) 42(2) 25(2) 21(2) -7(1) -4(1) 2(1) O(5) 85(2) 75(2) 55(2) 0(2) -32(2) -8(2) O(6) 51(2) 87(3) 66(2) -23(2) 5(2) -27(2) N(1) 54(2) 83(3) 78(3) -29(3) -12(2) -12(2) O(7) 122(3) 184(6) 109(4) -60(4) -42(3) -60(4) O(80) 48(1) 47(2) 37(1) 5(1) 18(1) 6(1) C(80) 52(2) 66(3) 40(3) 5(2) 9(2) 6(2) 151 C(81) 124(5) 63(4) 95(4) -18(4) 31(3) -30(3) N(80) 104(3) 70(3) 49(2) -1(2) 39(2) -8(2) C(82) 162(6) 98(5) 72(4) -7(3) 78(5) -34(4) C(83) 257(9) 64(4) 131(6) -24(4) 111(6) -39(5) O(90) 49(2) 45(2) 48(1) 8(1) 8(1) 23(1) C(90) 99(5) 95(5) 58(3) 48(3) 9(3) 25(5) C(91) 137(5) 46(3) 99(5) -7(3) -26(4) -4(3) N(90) 114(4) 128(6) 75(3) 18(3) 20(3) 101(4) C(92) 56(3) 119(6) 135(5) 13(5) -31(4) -19(4) C(93) 128(5) 114(5) 120(5) -8(5) 37(4) 76(4)
Table A 12: Hydrogen coordinates and isotropic displacement parameters for [Eu(NO3)(NDC)•2DMA]n
x (104) y (104) z (104) U(eq) (Å2 x 103) H(1) 8682 8724 7150 36 H(3) 11337 8310 6331 41 H(4) 11591 7402 7131 45 H(5) 11011 6691 8180 41 H(7) 8332 7087 8984 40 H(8) 8127 8044 8228 42 H(81A) 6088 9102 6849 141 H(81B) 6106 9096 6026 141 H(81C) 7065 8921 6449 141 H(82A) 5709 10564 7857 166 H(82B) 5194 9997 7360 166 H(82C) 6126 9767 7790 166 H(83A) 7233 11265 6644 226 H(83B) 7070 11247 7459 226 H(83C) 6211 11484 6960 226 H(91A) 8333 12305 5298 141 H(91B) 7432 12812 5136 141 H(91C) 7515 12422 5867 141 H(92A) 4959 11129 4874 155 152 H(92B) 5789 11050 4309 155 H(92C) 5865 10622 5020 155 H(93A) 4911 12118 5430 181 H(93B) 5745 12301 5971 181 H(93C) 5671 12740 5265 181
153
APPENDIX B
COMPUTATIONAL PARAMETERS 154 Table A 13: Ce(NO3)3•4H2O CASTEP parameters
Job Ce(NO3)3•4H2O Energy Module CASTEP Gateway Materials Studio Calculation: Single point energy Exchange-correlation functional local density approximation Pseudopotential representation reciprocal space plane wave basis set cut-off (eV) 280.0000 Grid size 1.5000 gmax size (Å-1) 12.8590 largest prime factor in FFT 5 finite basis correction none number of electrons 840.0 net charge 0.0000 net spin 0.0000 Number spin up 420.0 Number spin down 420.0 Population Analysis Cutoff 3.000 Å k-points 1 Point group, symmetry operators D2h, 8 Iterations 45 Time (s) 2496.1 CPU (cores) 8 Convergence (eV/atom) 6.72928721E-07 Energy (eV) -6.01232135E+04
Table A 14: Mulliken bond orders for Ce(NO3)3•4H2O
Species Label Species Label Population Bond Length N 22 -- O 99 0.75 1.21062 N 4 -- O 21 0.75 1.21062 N 19 -- O 86 0.75 1.21062 N 10 -- O 47 0.75 1.21062 N 7 -- O 34 0.75 1.21062 N 13 -- O 60 0.75 1.21062 N 1 -- O 8 0.75 1.21062 N 16 -- O 73 0.75 1.21062 N 24 -- O 93 0.74 1.21733 155 N 9 -- O 28 0.74 1.21733 N 6 -- O 15 0.74 1.21733 N 3 -- O 2 0.74 1.21733 N 21 -- O 80 0.74 1.21733 N 15 -- O 54 0.74 1.21733 N 18 -- O 67 0.74 1.21733 N 12 -- O 41 0.74 1.21733 N 17 -- O 70 0.75 1.22135 N 14 -- O 57 0.75 1.22135 N 8 -- O 31 0.75 1.22135 N 2 -- O 5 0.75 1.22135 N 23 -- O 96 0.75 1.22135 N 5 -- O 18 0.75 1.22135 N 11 -- O 44 0.75 1.22135 N 20 -- O 83 0.75 1.22135 N 16 -- O 76 0.68 1.24848 N 10 -- O 50 0.68 1.24848 N 22 -- O 102 0.68 1.24848 N 4 -- O 24 0.68 1.24848 N 1 -- O 11 0.68 1.24848 N 19 -- O 89 0.68 1.24848 N 13 -- O 63 0.68 1.24848 N 7 -- O 37 0.68 1.24848 N 21 -- O 82 0.67 1.25772 N 6 -- O 17 0.67 1.25772 N 15 -- O 56 0.67 1.25772 N 9 -- O 30 0.67 1.25772 N 18 -- O 69 0.67 1.25772 N 12 -- O 43 0.67 1.25772 N 24 -- O 95 0.67 1.25772 N 3 -- O 4 0.67 1.25772 N 13 -- O 62 0.65 1.26138 N 7 -- O 36 0.65 1.26138 N 22 -- O 101 0.65 1.26138 N 19 -- O 88 0.65 1.26138 N 16 -- O 75 0.65 1.26138 N 10 -- O 49 0.65 1.26138 N 1 -- O 10 0.65 1.26138 N 4 -- O 23 0.65 1.26138 156 N 24 -- O 104 0.66 1.26781 N 9 -- O 39 0.66 1.26781 N 12 -- O 52 0.66 1.26781 N 21 -- O 91 0.66 1.26781 N 15 -- O 65 0.66 1.26781 N 3 -- O 13 0.66 1.26781 N 18 -- O 78 0.66 1.26781 N 6 -- O 26 0.66 1.26781 N 20 -- O 81 0.66 1.26885 N 23 -- O 94 0.66 1.26885 N 17 -- O 68 0.66 1.26885 N 14 -- O 55 0.66 1.26885 N 11 -- O 42 0.66 1.26885 N 8 -- O 29 0.66 1.26885 N 5 -- O 16 0.66 1.26885 N 2 -- O 3 0.66 1.26885 N 14 -- O 64 0.68 1.2689 N 11 -- O 51 0.68 1.2689 N 2 -- O 12 0.68 1.2689 N 23 -- O 103 0.68 1.2689 N 17 -- O 77 0.68 1.2689 N 8 -- O 38 0.68 1.2689 N 20 -- O 90 0.68 1.2689 N 5 -- O 25 0.68 1.2689 O 101 -- O 102 -0.23 2.12117 O 75 -- O 76 -0.23 2.12117 O 62 -- O 63 -0.23 2.12117 O 49 -- O 50 -0.23 2.12117 O 36 -- O 37 -0.23 2.12117 O 23 -- O 24 -0.23 2.12117 O 88 -- O 89 -0.23 2.12117 O 10 -- O 11 -0.23 2.12117 O 99 -- O 102 -0.22 2.14216 O 34 -- O 37 -0.22 2.14216 O 8 -- O 11 -0.22 2.14216 O 86 -- O 89 -0.22 2.14216 O 73 -- O 76 -0.22 2.14216 O 60 -- O 63 -0.22 2.14216 O 47 -- O 50 -0.22 2.14216 157 O 21 -- O 24 -0.22 2.14216 O 16 -- O 18 -0.22 2.15533 O 55 -- O 57 -0.22 2.15533 O 94 -- O 96 -0.22 2.15533 O 81 -- O 83 -0.22 2.15533 O 68 -- O 70 -0.22 2.15533 O 42 -- O 44 -0.22 2.15533 O 29 -- O 31 -0.22 2.15533 O 3 -- O 5 -0.22 2.15533 O 80 -- O 91 -0.21 2.15684 O 93 -- O 104 -0.21 2.15684 O 41 -- O 52 -0.21 2.15684 O 28 -- O 39 -0.21 2.15684 O 54 -- O 65 -0.21 2.15684 O 15 -- O 26 -0.21 2.15684 O 67 -- O 78 -0.21 2.15684 O 2 -- O 13 -0.21 2.15684 O 54 -- O 56 -0.21 2.16141 O 41 -- O 43 -0.21 2.16141 O 80 -- O 82 -0.21 2.16141 O 67 -- O 69 -0.21 2.16141 O 28 -- O 30 -0.21 2.16141 O 2 -- O 4 -0.21 2.16141 O 15 -- O 17 -0.21 2.16141 O 93 -- O 95 -0.21 2.16141 O 30 -- O 39 -0.21 2.16306 O 82 -- O 91 -0.21 2.16306 O 95 -- O 104 -0.21 2.16306 O 69 -- O 78 -0.21 2.16306 O 17 -- O 26 -0.21 2.16306 O 4 -- O 13 -0.21 2.16306 O 56 -- O 65 -0.21 2.16306 O 43 -- O 52 -0.21 2.16306 O 55 -- O 64 -0.22 2.16678 O 42 -- O 51 -0.22 2.16678 O 94 -- O 103 -0.22 2.16678 O 68 -- O 77 -0.22 2.16678 O 29 -- O 38 -0.22 2.16678 O 3 -- O 12 -0.22 2.16678 158 O 81 -- O 90 -0.22 2.16678 O 16 -- O 25 -0.22 2.16678 O 60 -- O 62 -0.2 2.17723 O 99 -- O 101 -0.2 2.17723 O 86 -- O 88 -0.2 2.17723 O 34 -- O 36 -0.2 2.17723 O 21 -- O 23 -0.2 2.17723 O 8 -- O 10 -0.2 2.17723 O 73 -- O 75 -0.2 2.17723 O 47 -- O 49 -0.2 2.17723 O 57 -- O 64 -0.2 2.18594 O 44 -- O 51 -0.2 2.18594 O 5 -- O 12 -0.2 2.18594 O 70 -- O 77 -0.2 2.18594 O 31 -- O 38 -0.2 2.18594 O 96 -- O 103 -0.2 2.18594 O 83 -- O 90 -0.2 2.18594 O 18 -- O 25 -0.2 2.18594 O 87 -- Ce 7 0.22 2.48718 O 22 -- Ce 2 0.22 2.48718 O 9 -- Ce 1 0.22 2.48718 O 100 -- Ce 8 0.22 2.48718 O 74 -- Ce 6 0.22 2.48718 O 61 -- Ce 5 0.22 2.48718 O 48 -- Ce 4 0.22 2.48718 O 35 -- Ce 3 0.22 2.48718 O 98 -- Ce 8 0.21 2.49083 O 20 -- Ce 2 0.21 2.49083 O 72 -- Ce 6 0.21 2.49083 O 59 -- Ce 5 0.21 2.49083 O 46 -- Ce 4 0.21 2.49083 O 33 -- Ce 3 0.21 2.49083 O 85 -- Ce 7 0.21 2.49083 O 7 -- Ce 1 0.21 2.49083 O 92 -- Ce 8 0.22 2.52091 O 66 -- Ce 6 0.22 2.52091 O 53 -- Ce 5 0.22 2.52091 O 40 -- Ce 4 0.22 2.52091 O 27 -- Ce 3 0.22 2.52091 O 14 -- Ce 2 0.22 2.52091 159 O 1 -- Ce 1 0.22 2.52091 O 79 -- Ce 7 0.22 2.52091 O 58 -- Ce 5 0.21 2.56006 O 97 -- Ce 8 0.21 2.56006 O 84 -- Ce 7 0.21 2.56006 O 71 -- Ce 6 0.21 2.56006 O 45 -- Ce 4 0.21 2.56006 O 32 -- Ce 3 0.21 2.56006 O 19 -- Ce 2 0.21 2.56006 O 6 -- Ce 1 0.21 2.56006 O 26 -- Ce 2 0.11 2.59245 O 104 -- Ce 8 0.11 2.59245 O 65 -- Ce 5 0.11 2.59245 O 91 -- Ce 7 0.11 2.59245 O 78 -- Ce 6 0.11 2.59245 O 52 -- Ce 4 0.11 2.59245 O 39 -- Ce 3 0.11 2.59245 O 13 -- Ce 1 0.11 2.59245 O 16 -- Ce 2 0.14 2.60205 O 81 -- Ce 7 0.14 2.60205 O 68 -- Ce 6 0.14 2.60205 O 42 -- Ce 4 0.14 2.60205 O 29 -- Ce 3 0.14 2.60205 O 94 -- Ce 8 0.14 2.60205 O 55 -- Ce 5 0.14 2.60205 O 3 -- Ce 1 0.14 2.60205 O 82 -- Ce 7 0.11 2.6035 O 43 -- Ce 4 0.11 2.6035 O 69 -- Ce 6 0.11 2.6035 O 30 -- Ce 3 0.11 2.6035 O 17 -- Ce 2 0.11 2.6035 O 95 -- Ce 8 0.11 2.6035 O 56 -- Ce 5 0.11 2.6035 O 4 -- Ce 1 0.11 2.6035 O 101 -- Ce 8 0.11 2.62663 O 88 -- Ce 7 0.11 2.62663 O 75 -- Ce 6 0.11 2.62663 O 62 -- Ce 5 0.11 2.62663 O 49 -- Ce 4 0.11 2.62663 O 36 -- Ce 3 0.11 2.62663 O 23 -- Ce 2 0.11 2.62663 160 O 10 -- Ce 1 0.11 2.62663 O 76 -- Ce 6 0.1 2.65017 O 50 -- Ce 4 0.1 2.65017 O 102 -- Ce 8 0.1 2.65017 O 24 -- Ce 2 0.1 2.65017 O 89 -- Ce 7 0.1 2.65017 O 63 -- Ce 5 0.1 2.65017 O 37 -- Ce 3 0.1 2.65017 O 11 -- Ce 1 0.1 2.65017 O 90 -- Ce 1 0.15 2.68936 O 77 -- Ce 4 0.15 2.68936 O 38 -- Ce 5 0.15 2.68936 O 25 -- Ce 8 0.15 2.68936 O 64 -- Ce 3 0.15 2.68936 O 51 -- Ce 6 0.15 2.68936 O 12 -- Ce 7 0.15 2.68936 O 103 -- Ce 2 0.15 2.68936 O 66 -- O 70 0 2.74602 O 14 -- O 18 0 2.74602 O 79 -- O 83 0 2.74602 O 27 -- O 31 0 2.74602 O 53 -- O 57 0 2.74602 O 40 -- O 44 0 2.74602 O 1 -- O 5 0 2.74602 O 92 -- O 96 0 2.74602 O 25 -- O 102 -0.02 2.74673 O 50 -- O 77 -0.02 2.74673 O 24 -- O 103 -0.02 2.74673 O 38 -- O 63 -0.02 2.74673 O 12 -- O 89 -0.02 2.74673 O 11 -- O 90 -0.02 2.74673 O 51 -- O 76 -0.02 2.74673 O 37 -- O 64 -0.02 2.74673 O 76 -- O 78 -0.02 2.76154 O 11 -- O 13 -0.02 2.76154 O 102 -- O 104 -0.02 2.76154 O 89 -- O 91 -0.02 2.76154 O 63 -- O 65 -0.02 2.76154 O 50 -- O 52 -0.02 2.76154 O 37 -- O 39 -0.02 2.76154 O 24 -- O 26 -0.02 2.76154 161 O 20 -- O 96 0.02 2.77324 O 5 -- O 85 0.02 2.77324 O 46 -- O 70 0.02 2.77324 O 31 -- O 59 0.02 2.77324 O 18 -- O 98 0.02 2.77324 O 44 -- O 72 0.02 2.77324 O 33 -- O 57 0.02 2.77324 O 7 -- O 83 0.02 2.77324 O 42 -- O 50 -0.02 2.802 O 81 -- O 89 -0.02 2.802 O 68 -- O 76 -0.02 2.802 O 29 -- O 37 -0.02 2.802 O 55 -- O 63 -0.02 2.802 O 16 -- O 24 -0.02 2.802 O 94 -- O 102 -0.02 2.802 O 3 -- O 11 -0.02 2.802 O 35 -- O 75 0.01 2.80278 O 48 -- O 62 0.01 2.80278 O 49 -- O 61 0.01 2.80278 O 23 -- O 87 0.01 2.80278 O 22 -- O 88 0.01 2.80278 O 10 -- O 100 0.01 2.80278 O 36 -- O 74 0.01 2.80278 O 9 -- O 101 0.01 2.80278 O 3 -- O 74 0 2.80694 O 48 -- O 81 0 2.80694 O 9 -- O 68 0 2.80694 O 35 -- O 94 0 2.80694 O 29 -- O 100 0 2.80694 O 22 -- O 55 0 2.80694 O 16 -- O 61 0 2.80694 O 42 -- O 87 0 2.80694 O 92 -- O 101 -0.01 2.81333 O 40 -- O 49 -0.01 2.81333 O 14 -- O 23 -0.01 2.81333 O 66 -- O 75 -0.01 2.81333 O 53 -- O 62 -0.01 2.81333 O 27 -- O 36 -0.01 2.81333 O 79 -- O 88 -0.01 2.81333 O 1 -- O 10 -0.01 2.81333 O 38 -- O 58 0 2.81769 162 O 25 -- O 97 0 2.81769 O 6 -- O 90 0 2.81769 O 45 -- O 77 0 2.81769 O 19 -- O 103 0 2.81769 O 12 -- O 84 0 2.81769 O 51 -- O 71 0 2.81769 O 32 -- O 64 0 2.81769 O 95 -- O 100 -0.01 2.83957 O 30 -- O 35 -0.01 2.83957 O 56 -- O 61 -0.01 2.83957 O 17 -- O 22 -0.01 2.83957 O 82 -- O 87 -0.01 2.83957 O 43 -- O 48 -0.01 2.83957 O 69 -- O 74 -0.01 2.83957 O 4 -- O 9 -0.01 2.83957 O 92 -- O 98 0.05 2.84203 O 66 -- O 72 0.05 2.84203 O 53 -- O 59 0.05 2.84203 O 40 -- O 46 0.05 2.84203 O 27 -- O 33 0.05 2.84203 O 1 -- O 7 0.05 2.84203 O 14 -- O 20 0.05 2.84203 O 79 -- O 85 0.05 2.84203 O 17 -- O 79 0 2.85938 O 40 -- O 56 0 2.85938 O 43 -- O 53 0 2.85938 O 30 -- O 66 0 2.85938 O 1 -- O 95 0 2.85938 O 27 -- O 69 0 2.85938 O 14 -- O 82 0 2.85938 O 4 -- O 92 0 2.85938 O 27 -- O 102 0 2.9015 O 11 -- O 66 0 2.9015 O 40 -- O 89 0 2.9015 O 24 -- O 53 0 2.9015 O 37 -- O 92 0 2.9015 O 1 -- O 76 0 2.9015 O 14 -- O 63 0 2.9015 O 50 -- O 79 0 2.9015 O 78 -- O 85 -0.01 2.91005 O 13 -- O 46 -0.01 2.91005 163 O 20 -- O 39 -0.01 2.91005 O 72 -- O 91 -0.01 2.91005 O 7 -- O 52 -0.01 2.91005 O 65 -- O 98 -0.01 2.91005 O 59 -- O 104 -0.01 2.91005 O 26 -- O 33 -0.01 2.91005 N 19 -- O 12 -0.02 2.91643 N 13 -- O 38 -0.02 2.91643 N 4 -- O 103 -0.02 2.91643 N 22 -- O 25 -0.02 2.91643 N 10 -- O 77 -0.02 2.91643 N 1 -- O 90 -0.02 2.91643 N 7 -- O 64 -0.02 2.91643 N 16 -- O 51 -0.02 2.91643 O 10 -- O 90 -0.01 2.91775 O 38 -- O 62 -0.01 2.91775 O 49 -- O 77 -0.01 2.91775 O 25 -- O 101 -0.01 2.91775 O 23 -- O 103 -0.01 2.91775 O 12 -- O 88 -0.01 2.91775 O 51 -- O 75 -0.01 2.91775 O 36 -- O 64 -0.01 2.91775 O 6 -- O 54 0.01 2.91809 O 2 -- O 58 0.01 2.91809 O 41 -- O 97 0.01 2.91809 O 15 -- O 71 0.01 2.91809 O 45 -- O 93 0.01 2.91809 O 32 -- O 80 0.01 2.91809 O 28 -- O 84 0.01 2.91809 O 19 -- O 67 0.01 2.91809 O 94 -- O 95 -0.01 2.93261 O 81 -- O 82 -0.01 2.93261 O 16 -- O 17 -0.01 2.93261 O 55 -- O 56 -0.01 2.93261 O 29 -- O 30 -0.01 2.93261 O 3 -- O 4 -0.01 2.93261 O 68 -- O 69 -0.01 2.93261 O 42 -- O 43 -0.01 2.93261 O 73 -- O 84 0.01 2.97261 O 58 -- O 99 0.01 2.97261 O 21 -- O 32 0.01 2.97261 164 O 19 -- O 34 0.01 2.97261 O 8 -- O 45 0.01 2.97261 O 71 -- O 86 0.01 2.97261 O 6 -- O 47 0.01 2.97261 O 60 -- O 97 0.01 2.97261 O 97 -- O 100 0.04 2.97445 O 19 -- O 22 0.04 2.97445 O 84 -- O 87 0.04 2.97445 O 71 -- O 74 0.04 2.97445 O 45 -- O 48 0.04 2.97445 O 6 -- O 9 0.04 2.97445 O 58 -- O 61 0.04 2.97445 O 32 -- O 35 0.04 2.97445 O 72 -- O 74 0.03 2.97657 O 59 -- O 61 0.03 2.97657 O 46 -- O 48 0.03 2.97657 O 7 -- O 9 0.03 2.97657 O 98 -- O 100 0.03 2.97657 O 85 -- O 87 0.03 2.97657 O 33 -- O 35 0.03 2.97657 O 20 -- O 22 0.03 2.97657 O 69 -- O 71 0 2.9952 O 30 -- O 32 0 2.9952 O 82 -- O 84 0 2.9952 O 17 -- O 19 0 2.9952 O 43 -- O 45 0 2.9952 O 95 -- O 97 0 2.9952 O 56 -- O 58 0 2.9952 O 4 -- O 6 0 2.9952
Table A 15: Hirshfield charges for Ce(NO3)3•4H2O
Species Label Hirshfield Charge (e) N 8 0.28 N 1 0.26 N 9 0.27 N 2 0.28 N 10 0.26 N 3 0.27 N 11 0.28 N 4 0.26 N 12 0.27 N 5 0.28 N 13 0.26 N 6 0.27 N 14 0.28 N 7 0.26 N 15 0.27 165 N 16 0.26 O 33 -0.08 N 17 0.28 O 34 -0.09 N 18 0.27 O 35 -0.1 N 19 0.26 O 36 -0.09 N 20 0.28 O 37 -0.1 N 21 0.27 O 38 -0.1 N 22 0.26 O 39 -0.11 N 23 0.28 O 40 -0.09 N 24 0.27 O 41 -0.06 O 1 -0.09 O 42 -0.11 O 2 -0.06 O 43 -0.1 O 3 -0.11 O 44 -0.04 O 4 -0.1 O 45 -0.1 O 5 -0.04 O 46 -0.08 O 6 -0.1 O 47 -0.09 O 7 -0.08 O 48 -0.1 O 8 -0.09 O 49 -0.09 O 9 -0.1 O 50 -0.1 O 10 -0.09 O 51 -0.1 O 11 -0.1 O 52 -0.11 O 12 -0.1 O 53 -0.09 O 13 -0.11 O 54 -0.06 O 14 -0.09 O 55 -0.11 O 15 -0.06 O 56 -0.1 O 16 -0.11 O 57 -0.04 O 17 -0.1 O 58 -0.1 O 18 -0.04 O 59 -0.08 O 19 -0.1 O 60 -0.09 O 20 -0.08 O 61 -0.1 O 21 -0.09 O 62 -0.09 O 22 -0.1 O 63 -0.1 O 23 -0.09 O 64 -0.1 O 24 -0.1 O 65 -0.11 O 25 -0.1 O 66 -0.09 O 26 -0.11 O 67 -0.06 O 27 -0.09 O 68 -0.11 O 28 -0.06 O 69 -0.1 O 29 -0.11 O 70 -0.04 O 30 -0.1 O 71 -0.1 O 31 -0.04 O 72 -0.08 O 32 -0.1 O 73 -0.09 166 O 74 -0.1 O 94 -0.11 O 75 -0.09 O 95 -0.1 O 76 -0.1 O 96 -0.04 O 77 -0.1 O 97 -0.1 O 78 -0.11 O 98 -0.08 O 79 -0.09 O 99 -0.09 O 80 -0.06 O 100 -0.1 O 81 -0.11 O 101 -0.09 O 82 -0.1 O 102 -0.1 O 83 -0.04 O 103 -0.1 O 84 -0.1 O 104 -0.11 O 85 -0.08 Ce 1 0.35 O 86 -0.09 Ce 2 0.35 O 87 -0.1 Ce 3 0.35 O 88 -0.09 Ce 4 0.35 O 89 -0.1 Ce 5 0.35 O 90 -0.1 Ce 6 0.35 O 91 -0.11 Ce 7 0.35 O 92 -0.09 Ce 8 0.35 O 93 -0.06
Table A 16: [Ce(NO3)(NDC)]n CASTEP parameters
Job [Ce(NO3)(NDC)]n Energy Module CASTEP Gateway Materials Studio Calculation: Single point energy Exchange-correlation functional local density approximation Pseudopotential representation reciprocal space plane wave basis set cut-off (eV) 280.0000 Grid size 1.5000 gmax size (Å-1) 12.8590 largest prime factor in FFT 5 finite basis correction none number of electrons 904.0 net charge 0.0000 net spin 0.0000 Number spin up 452.0 Number spin down 452.0 Population analysis cutoff 3.000 Å 167 k-points 1 Point group, symmetry operators D2h, 8 Iterations 104 Time (s) 14659.44 CPU (cores) 8 Convergence (eV/atom) 5.17602532E-6 Energy (eV) -5.07300959E+4
Table A 17: Mulliken bond order analysis for [Ce(NO3)(NDC)]n
Bond Population Length (Å) H 024 -- C 046 0.83 0.94029 H 020 -- C 040 0.85 0.93845 H 030 -- C 058 0.83 0.94029 H 038 -- C 076 0.85 0.93845 H 042 -- C 082 0.83 0.94029 H 008 -- C 016 0.85 0.93845 H 035 -- C 068 0.89 0.94036 H 032 -- C 064 0.85 0.93845 H 023 -- C 044 0.89 0.94036 H 026 -- C 052 0.85 0.93845 H 005 -- C 008 0.89 0.94036 H 014 -- C 028 0.85 0.93845 H 047 -- C 092 0.89 0.94036 H 044 -- C 088 0.85 0.93845 H 041 -- C 080 0.89 0.94036 H 002 -- C 004 0.85 0.93845 H 029 -- C 056 0.89 0.94036 H 022 -- C 043 0.84 0.93885 H 017 -- C 032 0.89 0.94036 H 046 -- C 091 0.84 0.93885 H 011 -- C 020 0.89 0.94036 H 034 -- C 067 0.84 0.93885 H 043 -- C 087 0.91 0.94045 H 010 -- C 019 0.84 0.93885 H 025 -- C 051 0.91 0.94045 H 016 -- C 031 0.84 0.93885 H 031 -- C 063 0.91 0.94045 H 028 -- C 055 0.84 0.93885 H 037 -- C 075 0.91 0.94045 H 040 -- C 079 0.84 0.93885 H 007 -- C 015 0.91 0.94045 H 004 -- C 007 0.84 0.93885 H 001 -- C 003 0.91 0.94045 H 021 -- C 042 0.84 0.93916 H 019 -- C 039 0.91 0.94045 H 033 -- C 066 0.84 0.93916 H 013 -- C 027 0.91 0.94045 H 045 -- C 090 0.84 0.93916 N 006 -- O 042 0.77 1.21373 H 003 -- C 006 0.84 0.93916 N 002 -- O 014 0.77 1.21373 H 039 -- C 078 0.84 0.93916 N 005 -- O 035 0.77 1.21373 H 009 -- C 018 0.84 0.93916 N 007 -- O 049 0.77 1.21373 H 027 -- C 054 0.84 0.93916 N 003 -- O 021 0.77 1.21373 H 015 -- C 030 0.84 0.93916 N 001 -- O 007 0.77 1.21373 H 048 -- C 094 0.83 0.94029 N 008 -- O 056 0.77 1.21373 H 036 -- C 070 0.83 0.94029 N 004 -- O 028 0.77 1.21373 H 018 -- C 034 0.83 0.94029 C 071 -- O 011 0.92 1.24825 H 012 -- C 022 0.83 0.94029 C 047 -- O 053 0.92 1.24825 H 006 -- C 010 0.83 0.94029 C 083 -- O 018 0.92 1.24825 168 C 011 -- O 032 0.92 1.24825 C 073 -- O 017 0.93 1.25588 C 035 -- O 046 0.92 1.24825 C 001 -- O 031 0.93 1.25588 C 095 -- O 025 0.92 1.24825 C 037 -- O 052 0.93 1.25588 C 023 -- O 039 0.92 1.24825 C 085 -- O 024 0.93 1.25588 C 059 -- O 004 0.92 1.24825 C 039 -- C 040 1.14 1.36239 C 049 -- O 029 0.92 1.24906 C 015 -- C 016 1.14 1.36239 C 037 -- O 022 0.92 1.24906 C 063 -- C 064 1.14 1.36239 C 001 -- O 001 0.92 1.24906 C 027 -- C 028 1.14 1.36239 C 073 -- O 043 0.92 1.24906 C 051 -- C 052 1.14 1.36239 C 013 -- O 008 0.92 1.24906 C 087 -- C 088 1.14 1.36239 C 025 -- O 015 0.92 1.24906 C 003 -- C 004 1.14 1.36239 C 061 -- O 036 0.92 1.24906 C 075 -- C 076 1.14 1.36239 C 085 -- O 050 0.92 1.24906 C 055 -- C 056 1.14 1.36928 N 008 -- O 055 0.66 1.24927 C 079 -- C 080 1.14 1.36928 N 001 -- O 006 0.66 1.24927 C 007 -- C 008 1.14 1.36928 N 006 -- O 041 0.66 1.24927 C 043 -- C 044 1.14 1.36928 N 003 -- O 020 0.66 1.24927 C 067 -- C 068 1.14 1.36928 N 007 -- O 048 0.66 1.24927 C 091 -- C 092 1.14 1.36928 N 004 -- O 027 0.66 1.24927 C 019 -- C 020 1.14 1.36928 N 005 -- O 034 0.66 1.24927 C 031 -- C 032 1.14 1.36928 N 002 -- O 013 0.66 1.24927 C 012 -- C 030 1.15 1.38124 C 095 -- O 051 0.94 1.25374 C 006 -- C 036 1.15 1.38124 C 035 -- O 016 0.94 1.25374 C 024 -- C 042 1.15 1.38124 C 011 -- O 002 0.94 1.25374 C 072 -- C 090 1.15 1.38124 C 023 -- O 009 0.94 1.25374 C 018 -- C 048 1.15 1.38124 C 071 -- O 037 0.94 1.25374 C 054 -- C 084 1.15 1.38124 C 059 -- O 030 0.94 1.25374 C 066 -- C 096 1.15 1.38124 C 047 -- O 023 0.94 1.25374 C 060 -- C 078 1.15 1.38124 C 083 -- O 044 0.94 1.25374 C 074 -- C 082 1.14 1.39004 N 002 -- O 012 0.66 1.25393 C 026 -- C 034 1.14 1.39004 N 008 -- O 054 0.66 1.25393 C 038 -- C 046 1.14 1.39004 N 006 -- O 040 0.66 1.25393 C 050 -- C 058 1.14 1.39004 N 005 -- O 033 0.66 1.25393 C 014 -- C 022 1.14 1.39004 N 004 -- O 026 0.66 1.25393 C 002 -- C 010 1.14 1.39004 N 003 -- O 019 0.66 1.25393 C 086 -- C 094 1.14 1.39004 N 007 -- O 047 0.66 1.25393 C 062 -- C 070 1.14 1.39004 N 001 -- O 005 0.66 1.25393 C 081 -- C 082 1.05 1.40526 C 025 -- O 045 0.93 1.25588 C 057 -- C 058 1.05 1.40526 C 049 -- O 003 0.93 1.25588 C 045 -- C 046 1.05 1.40526 C 013 -- O 038 0.93 1.25588 C 009 -- C 010 1.05 1.40526 C 061 -- O 010 0.93 1.25588 C 093 -- C 094 1.05 1.40526 169 C 033 -- C 034 1.05 1.40526 C 089 -- C 090 1.04 1.41843 C 069 -- C 070 1.05 1.40526 C 005 -- C 006 1.04 1.41843 C 021 -- C 022 1.05 1.40526 C 053 -- C 057 1.06 1.4239 C 032 -- C 033 1.04 1.40903 C 077 -- C 081 1.06 1.4239 C 020 -- C 021 1.04 1.40903 C 065 -- C 069 1.06 1.4239 C 092 -- C 093 1.04 1.40903 C 017 -- C 021 1.06 1.4239 C 008 -- C 009 1.04 1.40903 C 089 -- C 093 1.06 1.4239 C 068 -- C 069 1.04 1.40903 C 029 -- C 033 1.06 1.4239 C 056 -- C 057 1.04 1.40903 C 005 -- C 009 1.06 1.4239 C 044 -- C 045 1.04 1.40903 C 041 -- C 045 1.06 1.4239 C 080 -- C 081 1.04 1.40903 C 085 -- C 086 0.85 1.49956 C 064 -- C 065 1.04 1.4131 C 001 -- C 002 0.85 1.49956 C 040 -- C 041 1.04 1.4131 C 073 -- C 074 0.85 1.49956 C 076 -- C 077 1.04 1.4131 C 049 -- C 050 0.85 1.49956 C 004 -- C 005 1.04 1.4131 C 013 -- C 014 0.85 1.49956 C 028 -- C 029 1.04 1.4131 C 037 -- C 038 0.85 1.49956 C 088 -- C 089 1.04 1.4131 C 061 -- C 062 0.85 1.49956 C 052 -- C 053 1.04 1.4131 C 025 -- C 026 0.85 1.49956 C 016 -- C 017 1.04 1.4131 C 035 -- C 036 0.84 1.50919 C 060 -- C 079 1.01 1.41317 C 083 -- C 084 0.84 1.50919 C 072 -- C 091 1.01 1.41317 C 011 -- C 012 0.84 1.50919 C 019 -- C 048 1.01 1.41317 C 023 -- C 024 0.84 1.50919 C 007 -- C 036 1.01 1.41317 C 095 -- C 096 0.84 1.50919 C 067 -- C 096 1.01 1.41317 C 047 -- C 048 0.84 1.50919 C 055 -- C 084 1.01 1.41317 C 059 -- C 060 0.84 1.50919 C 012 -- C 031 1.01 1.41317 C 071 -- C 072 0.84 1.50919 C 024 -- C 043 1.01 1.41317 H 002 -- C 003 -0.16 1.99717 C 074 -- C 075 1.02 1.41787 H 032 -- C 063 -0.16 1.99717 C 062 -- C 063 1.02 1.41787 H 014 -- C 027 -0.16 1.99717 C 026 -- C 027 1.02 1.41787 H 008 -- C 015 -0.16 1.99717 C 050 -- C 051 1.02 1.41787 H 020 -- C 039 -0.16 1.99717 C 002 -- C 003 1.02 1.41787 H 026 -- C 051 -0.16 1.99717 C 038 -- C 039 1.02 1.41787 H 044 -- C 087 -0.16 1.99717 C 086 -- C 087 1.02 1.41787 H 038 -- C 075 -0.16 1.99717 C 014 -- C 015 1.02 1.41787 H 031 -- C 064 -0.16 2.0067 C 029 -- C 030 1.04 1.41843 H 025 -- C 052 -0.16 2.0067 C 077 -- C 078 1.04 1.41843 H 001 -- C 004 -0.16 2.0067 C 041 -- C 042 1.04 1.41843 H 007 -- C 016 -0.16 2.0067 C 053 -- C 054 1.04 1.41843 H 043 -- C 088 -0.16 2.0067 C 017 -- C 018 1.04 1.41843 H 019 -- C 040 -0.16 2.0067 C 065 -- C 066 1.04 1.41843 H 037 -- C 076 -0.16 2.0067 170 H 013 -- C 028 -0.16 2.0067 H 020 -- C 041 -0.15 2.04398 H 010 -- C 020 -0.16 2.00734 H 002 -- C 005 -0.15 2.04398 H 046 -- C 092 -0.16 2.00734 H 032 -- C 065 -0.15 2.04398 H 034 -- C 068 -0.16 2.00734 H 044 -- C 089 -0.15 2.04398 H 022 -- C 044 -0.16 2.00734 H 038 -- C 077 -0.15 2.04398 H 028 -- C 056 -0.16 2.00734 H 014 -- C 029 -0.15 2.04398 H 004 -- C 008 -0.16 2.00734 H 026 -- C 053 -0.15 2.04398 H 040 -- C 080 -0.16 2.00734 H 008 -- C 017 -0.15 2.04398 H 016 -- C 032 -0.16 2.00734 H 035 -- C 069 -0.15 2.04496 H 029 -- C 055 -0.16 2.008 H 047 -- C 093 -0.15 2.04496 H 041 -- C 079 -0.16 2.008 H 017 -- C 033 -0.15 2.04496 H 023 -- C 043 -0.16 2.008 H 041 -- C 081 -0.15 2.04496 H 011 -- C 019 -0.16 2.008 H 029 -- C 057 -0.15 2.04496 H 035 -- C 067 -0.16 2.008 H 023 -- C 045 -0.15 2.04496 H 047 -- C 091 -0.16 2.008 H 005 -- C 009 -0.15 2.04496 H 005 -- C 007 -0.16 2.008 H 011 -- C 021 -0.15 2.04496 H 017 -- C 031 -0.16 2.008 H 046 -- C 072 -0.15 2.04803 H 003 -- C 036 -0.15 2.01856 H 022 -- C 024 -0.15 2.04803 H 033 -- C 096 -0.15 2.01856 H 040 -- C 060 -0.15 2.04803 H 015 -- C 012 -0.15 2.01856 H 004 -- C 036 -0.15 2.04803 H 045 -- C 072 -0.15 2.01856 H 028 -- C 084 -0.15 2.04803 H 039 -- C 060 -0.15 2.01856 H 034 -- C 096 -0.15 2.04803 H 021 -- C 024 -0.15 2.01856 H 010 -- C 048 -0.15 2.04803 H 009 -- C 048 -0.15 2.01856 H 016 -- C 012 -0.15 2.04803 H 027 -- C 084 -0.15 2.01856 H 021 -- C 041 -0.14 2.05201 H 048 -- C 086 -0.15 2.02448 H 033 -- C 065 -0.14 2.05201 H 012 -- C 014 -0.15 2.02448 H 015 -- C 029 -0.14 2.05201 H 030 -- C 050 -0.15 2.02448 H 003 -- C 005 -0.14 2.05201 H 018 -- C 026 -0.15 2.02448 H 045 -- C 089 -0.14 2.05201 H 042 -- C 074 -0.15 2.02448 H 039 -- C 077 -0.14 2.05201 H 024 -- C 038 -0.15 2.02448 H 027 -- C 053 -0.14 2.05201 H 036 -- C 062 -0.15 2.02448 H 009 -- C 017 -0.14 2.05201 H 006 -- C 002 -0.15 2.02448 H 043 -- C 086 -0.15 2.05737 H 024 -- C 045 -0.14 2.0394 H 013 -- C 026 -0.15 2.05737 H 048 -- C 093 -0.14 2.0394 H 025 -- C 050 -0.15 2.05737 H 030 -- C 057 -0.14 2.0394 H 031 -- C 062 -0.15 2.05737 H 012 -- C 021 -0.14 2.0394 H 019 -- C 038 -0.15 2.05737 H 042 -- C 081 -0.14 2.0394 H 007 -- C 014 -0.15 2.05737 H 006 -- C 009 -0.14 2.0394 H 001 -- C 002 -0.15 2.05737 H 018 -- C 033 -0.14 2.0394 H 037 -- C 074 -0.15 2.05737 H 036 -- C 069 -0.14 2.0394 O 040 -- O 041 -0.26 2.13111 171 O 012 -- O 013 -0.26 2.13111 H 007 -- H 008 -0.05 2.29394 O 054 -- O 055 -0.26 2.13111 H 037 -- H 038 -0.05 2.29394 O 047 -- O 048 -0.26 2.13111 H 013 -- H 014 -0.05 2.29394 O 019 -- O 020 -0.26 2.13111 H 019 -- H 020 -0.05 2.29394 O 026 -- O 027 -0.26 2.13111 H 001 -- H 002 -0.05 2.29394 O 033 -- O 034 -0.26 2.13111 H 043 -- H 044 -0.05 2.29394 O 005 -- O 006 -0.26 2.13111 H 028 -- H 029 -0.05 2.29917 O 055 -- O 056 -0.25 2.1384 H 046 -- H 047 -0.05 2.29917 O 013 -- O 014 -0.25 2.1384 H 034 -- H 035 -0.05 2.29917 O 006 -- O 007 -0.25 2.1384 H 010 -- H 011 -0.05 2.29917 O 020 -- O 021 -0.25 2.1384 H 022 -- H 023 -0.05 2.29917 O 041 -- O 042 -0.25 2.1384 H 004 -- H 005 -0.05 2.29917 O 048 -- O 049 -0.25 2.1384 H 040 -- H 041 -0.05 2.29917 O 034 -- O 035 -0.25 2.1384 H 016 -- H 017 -0.05 2.29917 O 027 -- O 028 -0.25 2.1384 C 048 -- O 053 -0.22 2.35687 O 054 -- O 056 -0.23 2.16601 C 084 -- O 018 -0.22 2.35687 O 040 -- O 042 -0.23 2.16601 C 036 -- O 046 -0.22 2.35687 O 047 -- O 049 -0.23 2.16601 C 096 -- O 025 -0.22 2.35687 O 019 -- O 021 -0.23 2.16601 C 024 -- O 039 -0.22 2.35687 O 012 -- O 014 -0.23 2.16601 C 012 -- O 032 -0.22 2.35687 O 005 -- O 007 -0.23 2.16601 C 072 -- O 011 -0.22 2.35687 O 033 -- O 035 -0.23 2.16601 C 060 -- O 004 -0.22 2.35687 O 026 -- O 028 -0.23 2.16601 C 036 -- O 016 -0.22 2.35972 O 024 -- O 050 -0.2 2.21108 C 024 -- O 009 -0.22 2.35972 O 022 -- O 052 -0.2 2.21108 C 084 -- O 044 -0.22 2.35972 O 003 -- O 029 -0.2 2.21108 C 012 -- O 002 -0.22 2.35972 O 015 -- O 045 -0.2 2.21108 C 060 -- O 030 -0.22 2.35972 O 001 -- O 031 -0.2 2.21108 C 048 -- O 023 -0.22 2.35972 O 017 -- O 043 -0.2 2.21108 C 096 -- O 051 -0.22 2.35972 O 010 -- O 036 -0.2 2.21108 C 072 -- O 037 -0.22 2.35972 O 008 -- O 038 -0.2 2.21108 C 050 -- O 029 -0.21 2.36104 O 009 -- O 039 -0.19 2.22768 C 038 -- O 022 -0.21 2.36104 O 002 -- O 032 -0.19 2.22768 C 086 -- O 050 -0.21 2.36104 O 018 -- O 044 -0.19 2.22768 C 002 -- O 001 -0.21 2.36104 O 011 -- O 037 -0.19 2.22768 C 026 -- O 015 -0.21 2.36104 O 025 -- O 051 -0.19 2.22768 C 014 -- O 008 -0.21 2.36104 O 023 -- O 053 -0.19 2.22768 C 062 -- O 036 -0.21 2.36104 O 004 -- O 030 -0.19 2.22768 C 074 -- O 043 -0.21 2.36104 O 016 -- O 046 -0.19 2.22768 C 074 -- O 017 -0.21 2.36448 H 031 -- H 032 -0.05 2.29394 C 038 -- O 052 -0.21 2.36448 H 025 -- H 026 -0.05 2.29394 C 002 -- O 031 -0.21 2.36448 172 C 062 -- O 010 -0.21 2.36448 C 012 -- C 032 -0.18 2.4169 C 086 -- O 024 -0.21 2.36448 C 068 -- C 096 -0.18 2.4169 C 014 -- O 038 -0.21 2.36448 C 060 -- C 080 -0.18 2.4169 C 026 -- O 045 -0.21 2.36448 C 056 -- C 084 -0.18 2.4169 C 050 -- O 003 -0.21 2.36448 C 006 -- C 007 -0.19 2.41789 C 050 -- C 052 -0.18 2.40498 C 078 -- C 079 -0.19 2.41789 C 038 -- C 040 -0.18 2.40498 C 090 -- C 091 -0.19 2.41789 C 074 -- C 076 -0.18 2.40498 C 054 -- C 055 -0.19 2.41789 C 014 -- C 016 -0.18 2.40498 C 018 -- C 019 -0.19 2.41789 C 002 -- C 004 -0.18 2.40498 C 030 -- C 031 -0.19 2.41789 C 062 -- C 064 -0.18 2.40498 C 066 -- C 067 -0.19 2.41789 C 086 -- C 088 -0.18 2.40498 C 042 -- C 043 -0.19 2.41789 C 026 -- C 028 -0.18 2.40498 C 003 -- C 005 -0.18 2.41969 H 008 -- H 029 -0.03 2.41065 C 063 -- C 065 -0.18 2.41969 H 023 -- H 038 -0.03 2.41065 C 015 -- C 017 -0.18 2.41969 H 020 -- H 041 -0.03 2.41065 C 087 -- C 089 -0.18 2.41969 H 005 -- H 032 -0.03 2.41065 C 051 -- C 053 -0.18 2.41969 H 014 -- H 047 -0.03 2.41065 C 027 -- C 029 -0.18 2.41969 H 002 -- H 035 -0.03 2.41065 C 075 -- C 077 -0.18 2.41969 H 011 -- H 026 -0.03 2.41065 C 039 -- C 041 -0.18 2.41969 H 017 -- H 044 -0.03 2.41065 C 077 -- C 082 -0.18 2.42934 C 055 -- C 057 -0.18 2.41457 C 005 -- C 010 -0.18 2.42934 C 019 -- C 021 -0.18 2.41457 C 089 -- C 094 -0.18 2.42934 C 091 -- C 093 -0.18 2.41457 C 053 -- C 058 -0.18 2.42934 C 079 -- C 081 -0.18 2.41457 C 065 -- C 070 -0.18 2.42934 C 067 -- C 069 -0.18 2.41457 C 029 -- C 034 -0.18 2.42934 C 031 -- C 033 -0.18 2.41457 C 017 -- C 022 -0.18 2.42934 C 007 -- C 009 -0.18 2.41457 C 041 -- C 046 -0.18 2.42934 C 043 -- C 045 -0.18 2.41457 C 027 -- C 034 -0.19 2.42982 O 036 -- Ce 006 0.29 2.41662 C 075 -- C 082 -0.19 2.42982 O 001 -- Ce 001 0.29 2.41662 C 051 -- C 058 -0.19 2.42982 O 029 -- Ce 005 0.29 2.41662 C 039 -- C 046 -0.19 2.42982 O 015 -- Ce 003 0.29 2.41662 C 003 -- C 010 -0.19 2.42982 O 043 -- Ce 007 0.29 2.41662 C 015 -- C 022 -0.19 2.42982 O 050 -- Ce 008 0.29 2.41662 C 063 -- C 070 -0.19 2.42982 O 022 -- Ce 004 0.29 2.41662 C 087 -- C 094 -0.19 2.42982 O 008 -- Ce 002 0.29 2.41662 C 012 -- C 029 -0.17 2.43312 C 072 -- C 092 -0.18 2.4169 C 024 -- C 041 -0.17 2.43312 C 024 -- C 044 -0.18 2.4169 C 065 -- C 096 -0.17 2.43312 C 020 -- C 048 -0.18 2.4169 C 005 -- C 036 -0.17 2.43312 C 008 -- C 036 -0.18 2.4169 C 072 -- C 089 -0.17 2.43312 173 C 053 -- C 084 -0.17 2.43312 C 005 -- C 008 -0.18 2.44622 C 017 -- C 048 -0.17 2.43312 C 053 -- C 056 -0.18 2.44622 C 060 -- C 077 -0.17 2.43312 O 023 -- Ce 004 0.28 2.44891 C 074 -- C 081 -0.17 2.43479 O 037 -- Ce 006 0.28 2.44891 C 050 -- C 057 -0.17 2.43479 O 044 -- Ce 007 0.28 2.44891 C 038 -- C 045 -0.17 2.43479 O 030 -- Ce 005 0.28 2.44891 C 002 -- C 009 -0.17 2.43479 O 051 -- Ce 008 0.28 2.44891 C 026 -- C 033 -0.17 2.43479 O 002 -- Ce 001 0.28 2.44891 C 062 -- C 069 -0.17 2.43479 O 016 -- Ce 003 0.28 2.44891 C 086 -- C 093 -0.17 2.43479 O 009 -- Ce 002 0.28 2.44891 C 014 -- C 021 -0.17 2.43479 C 076 -- C 081 -0.18 2.45028 O 011 -- Ce 002 0.25 2.44253 C 040 -- C 045 -0.18 2.45028 O 018 -- Ce 003 0.25 2.44253 C 004 -- C 009 -0.18 2.45028 O 046 -- Ce 007 0.25 2.44253 C 064 -- C 069 -0.18 2.45028 O 032 -- Ce 005 0.25 2.44253 C 052 -- C 057 -0.18 2.45028 O 004 -- Ce 001 0.25 2.44253 C 088 -- C 093 -0.18 2.45028 O 039 -- Ce 006 0.25 2.44253 C 028 -- C 033 -0.18 2.45028 O 025 -- Ce 004 0.25 2.44253 C 016 -- C 021 -0.18 2.45028 O 053 -- Ce 008 0.25 2.44253 C 056 -- C 058 -0.19 2.46326 C 078 -- C 081 -0.18 2.44503 C 008 -- C 010 -0.19 2.46326 C 066 -- C 069 -0.18 2.44503 C 044 -- C 046 -0.19 2.46326 C 018 -- C 021 -0.18 2.44503 C 032 -- C 034 -0.19 2.46326 C 030 -- C 033 -0.18 2.44503 C 092 -- C 094 -0.19 2.46326 C 054 -- C 057 -0.18 2.44503 C 068 -- C 070 -0.19 2.46326 C 090 -- C 093 -0.18 2.44503 C 080 -- C 082 -0.19 2.46326 C 006 -- C 009 -0.18 2.44503 C 020 -- C 022 -0.19 2.46326 C 042 -- C 045 -0.18 2.44503 C 064 -- C 066 -0.18 2.47472 O 045 -- Ce 007 0.17 2.44519 C 076 -- C 078 -0.18 2.47472 O 010 -- Ce 002 0.17 2.44519 C 028 -- C 030 -0.18 2.47472 O 024 -- Ce 004 0.17 2.44519 C 052 -- C 054 -0.18 2.47472 O 031 -- Ce 005 0.17 2.44519 C 040 -- C 042 -0.18 2.47472 O 017 -- Ce 003 0.17 2.44519 C 004 -- C 006 -0.18 2.47472 O 003 -- Ce 001 0.17 2.44519 C 088 -- C 090 -0.18 2.47472 O 052 -- Ce 008 0.17 2.44519 C 016 -- C 018 -0.18 2.47472 O 038 -- Ce 006 0.17 2.44519 H 003 -- O 046 0 2.48154 C 017 -- C 020 -0.18 2.44622 H 045 -- O 011 0 2.48154 C 041 -- C 044 -0.18 2.44622 H 021 -- O 039 0 2.48154 C 029 -- C 032 -0.18 2.44622 H 009 -- O 053 0 2.48154 C 077 -- C 080 -0.18 2.44622 H 015 -- O 032 0 2.48154 C 089 -- C 092 -0.18 2.44622 H 039 -- O 004 0 2.48154 C 065 -- C 068 -0.18 2.44622 H 027 -- O 018 0 2.48154 174 H 033 -- O 025 0 2.48154 H 005 -- H 031 -0.02 2.51062 H 047 -- H 048 -0.01 2.48728 H 013 -- H 047 -0.02 2.51062 H 017 -- H 018 -0.01 2.48728 H 019 -- H 041 -0.02 2.51062 H 035 -- H 036 -0.01 2.48728 H 017 -- H 043 -0.02 2.51062 H 023 -- H 024 -0.01 2.48728 H 011 -- H 025 -0.02 2.51062 H 041 -- H 042 -0.01 2.48728 H 023 -- H 037 -0.02 2.51062 H 029 -- H 030 -0.01 2.48728 H 007 -- H 029 -0.02 2.51062 H 005 -- H 006 -0.01 2.48728 H 001 -- H 035 -0.02 2.51062 H 011 -- H 012 -0.01 2.48728 H 004 -- O 016 0 2.52574 H 044 -- H 045 -0.02 2.48908 H 040 -- O 030 0 2.52574 H 032 -- H 033 -0.02 2.48908 H 034 -- O 051 0 2.52574 H 002 -- H 003 -0.02 2.48908 H 022 -- O 009 0 2.52574 H 026 -- H 027 -0.02 2.48908 H 046 -- O 037 0 2.52574 H 020 -- H 021 -0.02 2.48908 H 016 -- O 002 0 2.52574 H 014 -- H 015 -0.02 2.48908 H 010 -- O 023 0 2.52574 H 008 -- H 009 -0.02 2.48908 H 028 -- O 044 0 2.52574 H 038 -- H 039 -0.02 2.48908 C 073 -- C 075 -0.17 2.53561 C 037 -- C 046 -0.17 2.49572 C 037 -- C 039 -0.17 2.53561 C 085 -- C 094 -0.17 2.49572 C 001 -- C 003 -0.17 2.53561 C 049 -- C 058 -0.17 2.49572 C 049 -- C 051 -0.17 2.53561 C 073 -- C 082 -0.17 2.49572 C 085 -- C 087 -0.17 2.53561 C 013 -- C 022 -0.17 2.49572 C 013 -- C 015 -0.17 2.53561 C 001 -- C 010 -0.17 2.49572 C 061 -- C 063 -0.17 2.53561 C 025 -- C 034 -0.17 2.49572 C 025 -- C 027 -0.17 2.53561 C 061 -- C 070 -0.17 2.49572 C 011 -- C 031 -0.17 2.53572 C 071 -- C 090 -0.17 2.50182 C 007 -- C 035 -0.17 2.53572 C 011 -- C 030 -0.17 2.50182 C 019 -- C 047 -0.17 2.53572 C 023 -- C 042 -0.17 2.50182 C 071 -- C 091 -0.17 2.53572 C 006 -- C 035 -0.17 2.50182 C 023 -- C 043 -0.17 2.53572 C 054 -- C 083 -0.17 2.50182 C 067 -- C 095 -0.17 2.53572 C 018 -- C 047 -0.17 2.50182 C 055 -- C 083 -0.17 2.53572 C 066 -- C 095 -0.17 2.50182 C 059 -- C 079 -0.17 2.53572 C 059 -- C 078 -0.17 2.50182 H 019 -- O 022 0 2.57641 H 042 -- O 017 0 2.51051 H 025 -- O 029 0 2.57641 H 024 -- O 052 0 2.51051 H 013 -- O 015 0 2.57641 H 006 -- O 031 0 2.51051 H 001 -- O 001 0 2.57641 H 012 -- O 038 0 2.51051 H 007 -- O 008 0 2.57641 H 030 -- O 003 0 2.51051 H 043 -- O 050 0 2.57641 H 048 -- O 024 0 2.51051 H 037 -- O 043 0 2.57641 H 036 -- O 010 0 2.51051 H 031 -- O 036 0 2.57641 H 018 -- O 045 0 2.51051 O 055 -- Ce 008 0.14 2.6157 175 O 020 -- Ce 003 0.14 2.6157 H 032 -- C 066 -0.06 2.6504 O 048 -- Ce 007 0.14 2.6157 H 002 -- C 006 -0.06 2.6504 O 041 -- Ce 006 0.14 2.6157 H 026 -- C 054 -0.06 2.6504 O 027 -- Ce 004 0.14 2.6157 H 044 -- C 090 -0.06 2.6504 O 006 -- Ce 001 0.14 2.6157 H 014 -- C 030 -0.06 2.6504 O 034 -- Ce 005 0.14 2.6157 H 008 -- C 018 -0.06 2.6504 O 013 -- Ce 002 0.14 2.6157 H 035 -- C 070 -0.06 2.65057 O 054 -- Ce 008 0.15 2.63149 H 047 -- C 094 -0.06 2.65057 O 040 -- Ce 006 0.15 2.63149 H 029 -- C 058 -0.06 2.65057 O 026 -- Ce 004 0.15 2.63149 H 017 -- C 034 -0.06 2.65057 O 005 -- Ce 001 0.15 2.63149 H 011 -- C 022 -0.06 2.65057 O 033 -- Ce 005 0.15 2.63149 H 041 -- C 082 -0.06 2.65057 O 019 -- Ce 003 0.15 2.63149 H 005 -- C 010 -0.06 2.65057 O 012 -- Ce 002 0.15 2.63149 H 023 -- C 046 -0.06 2.65057 O 047 -- Ce 007 0.15 2.63149 H 033 -- C 064 -0.06 2.65661 H 048 -- C 085 -0.06 2.63469 H 015 -- C 028 -0.06 2.65661 H 006 -- C 001 -0.06 2.63469 H 045 -- C 088 -0.06 2.65661 H 042 -- C 073 -0.06 2.63469 H 003 -- C 004 -0.06 2.65661 H 030 -- C 049 -0.06 2.63469 H 021 -- C 040 -0.06 2.65661 H 036 -- C 061 -0.06 2.63469 H 027 -- C 052 -0.06 2.65661 H 024 -- C 037 -0.06 2.63469 H 009 -- C 016 -0.06 2.65661 H 018 -- C 025 -0.06 2.63469 H 039 -- C 076 -0.06 2.65661 H 012 -- C 013 -0.06 2.63469 H 004 -- C 035 -0.05 2.68586 H 015 -- C 011 -0.05 2.64398 H 034 -- C 095 -0.05 2.68586 H 003 -- C 035 -0.05 2.64398 H 040 -- C 059 -0.05 2.68586 H 027 -- C 083 -0.05 2.64398 H 028 -- C 083 -0.05 2.68586 H 021 -- C 023 -0.05 2.64398 H 022 -- C 023 -0.05 2.68586 H 045 -- C 071 -0.05 2.64398 H 010 -- C 047 -0.05 2.68586 H 033 -- C 095 -0.05 2.64398 H 046 -- C 071 -0.05 2.68586 H 039 -- C 059 -0.05 2.64398 H 016 -- C 011 -0.05 2.68586 H 009 -- C 047 -0.05 2.64398 H 037 -- C 073 -0.04 2.6993 H 024 -- C 044 -0.06 2.64483 H 019 -- C 037 -0.04 2.6993 H 030 -- C 056 -0.06 2.64483 H 001 -- C 001 -0.04 2.6993 H 012 -- C 020 -0.06 2.64483 H 043 -- C 085 -0.04 2.6993 H 018 -- C 032 -0.06 2.64483 H 013 -- C 025 -0.04 2.6993 H 006 -- C 008 -0.06 2.64483 H 025 -- C 049 -0.04 2.6993 H 048 -- C 092 -0.06 2.64483 H 007 -- C 013 -0.04 2.6993 H 042 -- C 080 -0.06 2.64483 H 031 -- C 061 -0.04 2.6993 H 036 -- C 068 -0.06 2.64483 C 006 -- O 046 -0.05 2.78122 H 038 -- C 078 -0.06 2.6504 C 042 -- O 039 -0.05 2.78122 H 020 -- C 042 -0.06 2.6504 C 018 -- O 053 -0.05 2.78122 176 C 090 -- O 011 -0.05 2.78122 C 069 -- C 096 -0.12 2.80824 C 030 -- O 032 -0.05 2.78122 C 009 -- C 036 -0.12 2.80824 C 054 -- O 018 -0.05 2.78122 C 057 -- C 084 -0.12 2.80824 C 066 -- O 025 -0.05 2.78122 C 060 -- C 081 -0.12 2.80824 C 078 -- O 004 -0.05 2.78122 C 041 -- C 043 -0.12 2.80857 C 040 -- C 046 -0.13 2.78668 C 053 -- C 055 -0.12 2.80857 C 052 -- C 058 -0.13 2.78668 C 005 -- C 007 -0.12 2.80857 C 004 -- C 010 -0.13 2.78668 C 017 -- C 019 -0.12 2.80857 C 076 -- C 082 -0.13 2.78668 C 089 -- C 091 -0.12 2.80857 C 064 -- C 070 -0.13 2.78668 C 077 -- C 079 -0.12 2.80857 C 028 -- C 034 -0.13 2.78668 C 029 -- C 031 -0.12 2.80857 C 016 -- C 022 -0.13 2.78668 C 065 -- C 067 -0.12 2.80857 C 088 -- C 094 -0.13 2.78668 C 007 -- O 016 -0.04 2.80875 C 022 -- O 038 -0.04 2.79496 C 031 -- O 002 -0.04 2.80875 C 082 -- O 017 -0.04 2.79496 C 019 -- O 023 -0.04 2.80875 C 046 -- O 052 -0.04 2.79496 C 091 -- O 037 -0.04 2.80875 C 094 -- O 024 -0.04 2.79496 C 079 -- O 030 -0.04 2.80875 C 034 -- O 045 -0.04 2.79496 C 043 -- O 009 -0.04 2.80875 C 010 -- O 031 -0.04 2.79496 C 067 -- O 051 -0.04 2.80875 C 058 -- O 003 -0.04 2.79496 C 055 -- O 044 -0.04 2.80875 C 070 -- O 010 -0.04 2.79496 C 063 -- C 069 -0.11 2.82324 C 078 -- C 080 -0.13 2.79692 C 039 -- C 045 -0.11 2.82324 C 066 -- C 068 -0.13 2.79692 C 027 -- C 033 -0.11 2.82324 C 018 -- C 020 -0.13 2.79692 C 003 -- C 009 -0.11 2.82324 C 054 -- C 056 -0.13 2.79692 C 051 -- C 057 -0.11 2.82324 C 090 -- C 092 -0.13 2.79692 C 015 -- C 021 -0.11 2.82324 C 030 -- C 032 -0.13 2.79692 C 087 -- C 093 -0.11 2.82324 C 006 -- C 008 -0.13 2.79692 C 075 -- C 081 -0.11 2.82324 C 042 -- C 044 -0.13 2.79692 C 051 -- O 029 -0.03 2.84194 C 074 -- C 077 -0.12 2.801 C 087 -- O 050 -0.03 2.84194 C 014 -- C 017 -0.12 2.801 C 075 -- O 043 -0.03 2.84194 C 050 -- C 053 -0.12 2.801 C 003 -- O 001 -0.03 2.84194 C 062 -- C 065 -0.12 2.801 C 039 -- O 022 -0.03 2.84194 C 002 -- C 005 -0.12 2.801 C 027 -- O 015 -0.03 2.84194 C 026 -- C 029 -0.12 2.801 C 015 -- O 008 -0.03 2.84194 C 086 -- C 089 -0.12 2.801 C 063 -- O 036 -0.03 2.84194 C 038 -- C 041 -0.12 2.801 H 038 -- C 044 -0.03 2.93642 C 072 -- C 093 -0.12 2.80824 H 020 -- C 080 -0.03 2.93642 C 012 -- C 033 -0.12 2.80824 H 008 -- C 056 -0.03 2.93642 C 021 -- C 048 -0.12 2.80824 H 032 -- C 008 -0.03 2.93642 C 024 -- C 045 -0.12 2.80824 H 026 -- C 020 -0.03 2.93642 177 H 014 -- C 092 -0.03 2.93642 O 044 -- O 048 -0.01 2.98082 H 002 -- C 068 -0.03 2.93642 O 002 -- O 006 -0.01 2.98082 H 044 -- C 032 -0.03 2.93642 O 030 -- O 034 -0.01 2.98082 H 029 -- C 016 -0.03 2.97904 O 016 -- O 020 -0.01 2.98082 H 023 -- C 076 -0.03 2.97904 O 009 -- O 013 -0.01 2.98082 H 035 -- C 004 -0.03 2.97904 O 044 -- O 047 -0.01 2.9969 H 011 -- C 052 -0.03 2.97904 O 037 -- O 040 -0.01 2.9969 H 047 -- C 028 -0.03 2.97904 O 023 -- O 026 -0.01 2.9969 H 041 -- C 040 -0.03 2.97904 O 009 -- O 012 -0.01 2.9969 H 017 -- C 088 -0.03 2.97904 O 002 -- O 005 -0.01 2.9969 H 005 -- C 064 -0.03 2.97904 O 051 -- O 054 -0.01 2.9969 O 037 -- O 041 -0.01 2.98082 O 030 -- O 033 -0.01 2.9969 O 023 -- O 027 -0.01 2.98082 O 016 -- O 019 -0.01 2.9969 O 051 -- O 055 -0.01 2.98082
Table A 18: Hirshfield charges on [Ce(NO3)(NDC)]n
Species Hirshfield Charge (e) H 24 0.04 H 1 0.04 H 25 0.04 H 2 0.04 H 26 0.04 H 3 0.04 H 27 0.04 H 4 0.04 H 28 0.04 H 5 0.05 H 29 0.05 H 6 0.04 H 30 0.04 H 7 0.04 H 31 0.04 H 8 0.04 H 32 0.04 H 9 0.04 H 33 0.04 H 10 0.04 H 34 0.04 H 11 0.05 H 35 0.05 H 12 0.04 H 36 0.04 H 13 0.04 H 37 0.04 H 14 0.04 H 38 0.04 H 15 0.04 H 39 0.04 H 16 0.04 H 40 0.04 H 17 0.05 H 41 0.05 H 18 0.04 H 42 0.04 H 19 0.04 H 43 0.04 H 20 0.04 H 44 0.04 H 21 0.04 H 45 0.04 H 22 0.04 H 46 0.04 H 23 0.05 H 47 0.05 178 H 48 0.04 C 41 0.02 C 1 0.19 C 42 -0.04 C 2 0 C 43 -0.05 C 3 -0.05 C 44 -0.05 C 4 -0.04 C 45 0.02 C 5 0.02 C 46 -0.04 C 6 -0.04 C 47 0.19 C 7 -0.05 C 48 0 C 8 -0.05 C 49 0.19 C 9 0.02 C 50 0 C 10 -0.04 C 51 -0.05 C 11 0.19 C 52 -0.04 C 12 0 C 53 0.02 C 13 0.19 C 54 -0.04 C 14 0 C 55 -0.05 C 15 -0.05 C 56 -0.05 C 16 -0.04 C 57 0.02 C 17 0.02 C 58 -0.04 C 18 -0.04 C 59 0.19 C 19 -0.05 C 60 0 C 20 -0.05 C 61 0.19 C 21 0.02 C 62 0 C 22 -0.04 C 63 -0.05 C 23 0.19 C 64 -0.04 C 24 0 C 65 0.02 C 25 0.19 C 66 -0.04 C 26 0 C 67 -0.05 C 27 -0.05 C 68 -0.05 C 28 -0.04 C 69 0.02 C 29 0.02 C 70 -0.04 C 30 -0.04 C 71 0.19 C 31 -0.05 C 72 0 C 32 -0.05 C 73 0.19 C 33 0.02 C 74 0 C 34 -0.04 C 75 -0.05 C 35 0.19 C 76 -0.04 C 36 0 C 77 0.02 C 37 0.19 C 78 -0.04 C 38 0 C 79 -0.05 C 39 -0.05 C 80 -0.05 C 40 -0.04 C 81 0.02 179 C 82 -0.04 O 19 -0.22 C 83 0.19 O 20 -0.22 C 84 0 O 21 -0.22 C 85 0.19 O 22 -0.21 C 86 0 O 23 -0.21 C 87 -0.05 O 24 -0.23 C 88 -0.04 O 25 -0.23 C 89 0.02 O 26 -0.22 C 90 -0.04 O 27 -0.22 C 91 -0.05 O 28 -0.22 C 92 -0.05 O 29 -0.21 C 93 0.02 O 30 -0.21 C 94 -0.04 O 31 -0.23 C 95 0.19 O 32 -0.23 C 96 0 O 33 -0.22 N 1 0.23 O 34 -0.22 N 2 0.23 O 35 -0.22 N 3 0.23 O 36 -0.21 N 4 0.23 O 37 -0.21 N 5 0.23 O 38 -0.23 N 6 0.23 O 39 -0.23 N 7 0.23 O 40 -0.22 N 8 0.23 O 41 -0.22 O 1 -0.21 O 42 -0.22 O 2 -0.21 O 43 -0.21 O 3 -0.23 O 44 -0.21 O 4 -0.23 O 45 -0.23 O 5 -0.22 O 46 -0.23 O 6 -0.22 O 47 -0.22 O 7 -0.22 O 48 -0.22 O 8 -0.21 O 49 -0.22 O 9 -0.21 O 50 -0.21 O 10 -0.23 O 51 -0.21 O 11 -0.23 O 52 -0.23 O 12 -0.22 O 53 -0.23 O 13 -0.22 O 54 -0.22 O 14 -0.22 O 55 -0.22 O 15 -0.21 O 56 -0.22 O 16 -0.21 Ce 1 0.69 O 17 -0.23 Ce 2 0.69 O 18 -0.23 Ce 3 0.69 180 Ce 4 0.69 Ce 7 0.69 Ce 5 0.69 Ce 8 0.69 Ce 6 0.69