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Synthesis and Characterization of Host-Guest Complexes: Metal-Organic Nanocapsules Using Aryl-Substituted Pyrogallol[4]Arenes

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Synthesis and Characterization of Host-Guest Complexes: Metal-Organic Nanocapsules Using Aryl-Substituted Pyrogallol[4]Arenes Synthesis and Characterization of Host-Guest Complexes: Metal-Organic Nanocapsules Using Aryl-Substituted Pyrogallol[4]arenes A Dissertation Presented to The Faculty of the Graduate School University of Missouri-Columbia In Partial Fulfillment Of the Requirements for the Degree Doctor of Philosophy By Andrew K. Maerz Dr. Jerry L. Atwood, Dissertation Supervisor July 2011 The undersigned, appointed by the dean of the Graduate School, have examined the dissertation entitled Synthesis and Characterization of Host-Guest Complexes: Metal- Organic Nanocapsules Using Aryl-Substituted Pyrogallol[4]arenes Presented by Andrew K. Maerz A candidate for the degree of doctor of philosophy of Chemistry, And hereby certify that, in their opinion, it is worthy of acceptance Professor Jerry L. Atwood (CHAIR) Professor Peter A. Tipton (OUTSIDE MEMBER) Professor Jason W. Cooley (MEMBER) Professor Carol A. Deakyne (MEMBER) Professor Paul A. Sharp (MEMBER) ACKNOWLEDGMENTS I am forever indebted to my dissertation supervisor, Professor Jerry L. Atwood, for giving me the opportunity to prove my worth and join his research group. His guidance and generous support have allowed me to grow, not only from my experiences here but also from my experiences from my travels to Durham, England and presenting throughout the US. His motivation and charisma are two things I greatly respect about him and hope to take with me on my adventure into the chemical industry. I am also grateful to all the members of my committee, Prof. Carol A. Deakyne, Prof. Jason W. Cooley, Prof. Paul A. Sharp, and Prof. Peter A. Tipton for their academic advice and guidance. I would like to especially thank Prof. Carol A. Deakyne for all of her support and thoughtful discussion pertaining to this work. I would like to extend my thanks to Dr. Charles Barnes for his patience and assistance with the extremely disordered X-ray crystallographic structures as well as to Dr. Wei Wycoff for her assistance using multiple techniques to characterize samples through NMR. I would also like to thank Dr. Brian Mooney for his help and guidance while using the MALDI Voyager DE-Pro MS; the work in this field has given me many things to ponder. Special thanks are in order to all of the members of the Atwood research group. I am also thankful for the entire Department of Chemistry at the University of Missouri-Columbia. I would also like to thank all of my family, especially my mother and father who have sacrificed so much for me. And lastly, I would like to thank my wife, Tanya M. Maerz, for her constant support and reassurance when research would take a turn for the worse. Without her, none of this would have been possible. ii TABLE OF CONTENTS ACKNOWLEDGMENTS ii LIST OF TABLES viii LIST OF FIGURES ix LIST OF SCHEMES xix ABSTRACT xx 1 Supramolecular Chemistry: The Art of Self-Assembly and Interaction 1.1 Supramolecular chemistry: by the book 1 1.1.1 Preorganization and complementartity 3 1.1.2 Building blocks in host-guest chemistry 5 1.1.2.1 Cyclodextrins 6 1.1.2.2 Gylcoluril-Based Hosts (Specifically Cucurbiturils) 8 1.1.2.3 1,3,5-triethylbenzene “pinwheel” 10 1.1.2.4 Kohnkenes 11 1.1.2.5 Cyclophanes 12 1.1.2.5.1 Cyclotriveratrylenes (CTVs) 13 1.1.2.5.2 Calix[4]arenes 14 1.2 The Glue that Holds Supramolecular Chemistry Together: Non-covalent Interactions 18 iii 1.2.1 Static Model Electrostatic Interactions 19 1.2.2 Induced-Dipole Interactions 20 1.2.3 Cation-π, Anion-π, and π-π Interactions 21 1.2.4 Hydrogen Bonding 23 2 Synthesis and Characterization of Aryl-substituted Pyrogallol[4]arenes 2.1 Introduction: history of resorcin[4]arenes and pyrogallol[4]arenes 25 2.1.1 Previously reported structures 28 2.2 Thermodynamics: a computational study 31 2.3 Experimental Studies: Synthesis and characterization of selected C- arylpyrogallol[4]arenes 37 2.3.1 Synthesis and characterization of C-phenylpyrogallol[4]arene 37 2.3.2 Mono-substituted C-arylpyrogallol[4]arenes 42 2.3.2.1 Analysis of C-4-methylphenylpyrogallol[4]arene 2.2 and C-4-ethylphenylpyrogallol[4]arene 2.3 45 2.3.2.2 Analysis of C-3-nitrophenylpyrogallol[4]arene 2.4 and C-4- nitrophenylpyrogallol[4]arene 2.5 48 iv 2.3.2.3 Analysis of C-3-hydroxyphenylpyrogallol[4]arene 2.6 and C-4-hydroxyphenylpyrogallol[4]arene 2.7 50 2.3.2.4 Analysis of C-2-methoxyphenylpyrogallol[4]arene 2.8 and C-4-methoxyphenylpyrogallol[4]arene 2.9 57 2.3.2.5 Analysis of C-4-propoxyphenylpyrogallol[4]arene 2.10 59 2.3.3 Di- substituted C-arylpyrogallol[4]arenes 61 2.3.3.1 Analysis of C-2,3-dimethoxyphenylpyrogallol[4]arene 2.12 and C-2,4-dimethoxyphenylpyrogallol[4]arene 2.13 61 2.3.3.2 Analysis of C-3,4-dimethylphenylpyrogallol[4]- arene 2.14 66 2.3.3.3 Analysis of C-3,5-dihydroxyphenylpyrogallol[4]-arene 2.15 67 2.3.4 Tri- substituted C-arylpyrogallol[4]arenes 69 2.4 Inherent instability and decomposition of pyrogallol[4]arenes 73 2.5 Conclusions 78 2.6 Future studies 78 2.7 Experimental Data 79 3 Formation of Metal-Organic Nanocapsules (MONCs) Through Conformational Flipping v 3.1 Influences in the design of dimeric nanocapsule formation 92 3.2 Synthesis and characterization of dimeric zinc nanocapsules 98 3.2.1 Synthesis of MONCs formed from C-phenylpyrogallol[4]- arene 100 3.2.2 Synthesis of MONCs formed from substituted C- arylpyrgallol[4]arene 104 3.3 Solid-state study of the MONCs formed from C-arylpyroallol[4]arenes 105 3.4 Guest characterization and kinetic formation 111 3.5 Conclusions 116 3.6 Future studies 116 4 The Use of Mixed Macrocycles in New and Diverse Supramolecular Architecture Via Solvent Mediation 4.1 Introduction and synthesis of mixed macrocycles 118 4.2 Synthesis of organic nanostrucutres using mixed macrocycles 121 4.3 Solid-state investigation of various super structure using mixed macrocycles as building blocks 123 4.4 Conclusions 129 vi 4.5 Experimental Data 129 Appendix A 131 References 144 VITA 156 vii LIST OF TABLES Table 1.1: Key characteristics and parameters of α-, β-, and γ-cyclodextrins. 8 Table 1.2: Contributions of three distinct hydrogen bonding environments 24 Table 2.1: Previously reported C-arylpyrogallol[4]arenes in various solvent systems, each in the chair conformation. 29 Table 2.2: Computational data at both the B3LYP/6-31G(d) and MP2/6-31G(d) levels. Bold lettering indicates the conformers of particular interest, with red numbers indicating the most stable conformer at that particular level of calculation. 34 Table 2.3: Enthalpies and free energies using the polarizable continuum model (PCM B3LYP/6-31G(d)) to test solvent effects. 36 Table 2.4: Complete list of all synthesized C-arylpyrogallol[4]arenes, their isolated conformations and the solvent systems. Boxes highlighted in blue are macrocycles that have been isolated as both the chair and boat conformers. 44 Table 4.1: Solved partial occupancies of the central oxygen atom of compounds 4.1 and 4.2 124 viii LIST OF FIGURES Figure 1.1: a) Schematic representation of the complexation of cavitands into an inclusion host-guest complex known as a caviplex. b) Schematic representation of the complexation of clathrands into an inclusion host-guest complex known as a clathrate, where the gaps between clathrands create the cavity only accessible in the solid- state. 3 Figure 1.2: Comparison of preorganization effects: a) vs. b), macrocyclic; c) vs. d), macrobicyclic; and e) vs. f) vs. g), complementarity. 5 Figure 1.3: a-c) α,β,γ-cyclodextrins consisting of six (6), seven (7), and eight (8) glucose units, respectively. d) 1,4-glycosidic link which joins adjacent D-glucopyranoside units. 7 Figure 1.4: Schematic representation of a) glycoluril and b) diphenylglycoluril. c) Crystallographic image of a hydrogen-bonded dimeric sphere based on two (2) diphenylglycoluril units; guest H2O molecule omitted for clarity. 9 Figure 1.5: a) Schematic representation of a cucurbituril with six (6) glycoluril base units (CB[6]). b) Crystallographic image of CB[6] showing the guest accessible cavity of 5.8 Å in diameter. 9 Figure 1.6: Schematic representation of tripodal anionic receptors using a 1,3,5- trisubstituted-2,4,6-trimethyl- or triethylbenzene scaffold. a) Uses three imidazolium ix rings to enhance binding of anionic guests, b) Uses boronic acid for use in IDAs, c) Uses tripodal tris(urea) cationic receptors for anionic sensors. 10 Figure 1.7: Schematic representation of a) kohnkene precursor b) kohnkene. 12 Figure 1.8: Schematic representation of a) cyclotriveratrylene (CTV) and b) expanded CTV-based cavitand. 14 Figure 1.9: Possible conformations of calix[4]arenes. 15 Figure 1.10: Commonly occurring members of the calixarene family: a) calix[4]arene, b) calix[6]arene, and c) calix[8]arene. 16 Figure 1.11: a) Crystallographic image of covalently linked dimeric calixarenes. b) Crystallographic image of a trimeric superstructure consisting of three (3) calixarenes, shown in red, blue, and turquoise, linked by samarium in green. c) Hexameric superstructure consisting of six (6) resorcin[4]arenes. 18 Figure 1.12: Examples of different types of electrostatic interactions a-c) ion-dipole, d) type 1 dipole-dipole, and e) type 2 dipole-dipole interactions. 20 Figure 1.13: Interacting π-quadrupoles illustrating the repulsive and attractive forces associated with different alignment motifs. 22 Figure 2.1: a) Possible conformers of resorcin[4]arene. b) Representation of the four (4) principle diastereomers.
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