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Metal-Organic Frameworks of Pyrazolate Derivatives: Synthesis and Applications for Chemical Sensing, Gas Separation, and Catalysis

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Metal-Organic Frameworks of Pyrazolate Derivatives: Synthesis and Applications for Chemical Sensing, Gas Separation, and Catalysis Metal-Organic Frameworks of Pyrazolate Derivatives: Synthesis and Applications for Chemical Sensing, Gas Separation, and Catalysis by Charlie Eric William Kivi A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy Department of Chemistry University of Toronto © Copyright by Charlie E. Kivi, 2017 Metal-Organic Frameworks of Pyrazolate Derivatives: Synthesis and Applications for Chemical Sensing, Gas Separation, and Catalysis Charlie Eric William Kivi Doctor of Philosophy Department of Chemistry University of Toronto 2017 Abstract In this work we examine the structure and applications of metal-organic frameworks (MOFs) synthesized from pyrazolate derivatives. In total, six pyrazolate ligands were examined: 4-(4- (3,5-dimethyl-1H-pyrazol-4-yl)phenyl)pyridine (HL), 1,1’-methylenebis(3,5-dimethyl-1H- pyrazolyl-4-carboxylic acid) (H2BPM), triethyl-1,1',1''-methanetriyltris(3,5-dimethyl-1H- pyrazole-4-carboxylate) (TPM-1), triethyl-4,4',4''-(methanetriyltris[3,5-dimethyl-1H-pyrazole- 1,4-diyl])tribenzoate (TPM-2), 1,1',1'',1'''-(propane-1,1,3,3-tetrayl)tetrakis(3,5-dimethyl-1H- pyrazole-4-carboxylic acid) (H4TPP), tetraethyl-1,1',1'',1'''-(1,4-phenylenebis[methanetriyl]) tetrakis(3,5-dimethyl-1H-pyrazole-4-carboxylate)pyridinephenylpyrazole (TPX). These ligands were used to synthesize a variety of MOFs that were subsequently investigated for luminescent sensing, gas storage, and catalytic performance. In Chapter 2, three MOFs synthesized from the reaction of HL and CuX (X = Br, I) were investigated. These materials were found to form MOFs which contained the luminescent trinuclear Cu(I) pyrazolate unit. Only CuBr and HL alone resulted in a MOF of sufficient purity and stability to permit evaluation as a luminescent sensor. Experiments with various volatile ii organic compounds revealed turn-on (luminescence enhancement) behaviour for ethyl acetate, pentane, and benzene and turn-off (luminescence quenching) behaviour for diethyl ether and chloroform for this material. In Chapters 3 and 4, ten MOFs are described. These were synthesized from H2BPM and metal- acetate salts. Chapter 3 encompassed two MOFs: [Ni(BPM)]n∙xDMSO and [Cd(BPM)]n∙xDMSO. These MOFs are isostructural, microporous materials. Evacuation of the pores led to collapse of the [Cd(BPM)]n∙xDMSO material but [Ni(BPM)]n∙xDMSO proved to be permanently porous. Further investigations revealed [Ni(BPM)]n∙xDMSO selectively adsorbed methane over nitrogen indicating it may serve as a porous material for coal mine methane capture. Chapter 4 investigated the many other structures H2BPM can assume in the presence of manganese, cobalt, iron, copper, and europium. Cobalt in particular proved highly tunable with 4 separate structures being synthesized such as [Co2(BPM)2(H2O)4(Bpy)0.5]n∙2DMF∙2(H2O). This was achieved through varying the synthetic conditions. [Co2(BPM)2(H2O)4(Bpy)0.5]n∙2DMF∙2(H2O)and [Eu(BPM)(OAc)]n were further investigated for the oxidation of olefins and luminescence respectively. In Chapter 5, metal complexes Mo(TPM-1)(CO)3, Mo(TPM-2)(CO)3, Pd2(H4TPP)Cl4, and Pd2(TPX)Cl4 were synthesized. The catalytic performance of Mo(TPM-1)(CO)3 was evaluated and found to be effective for the oxidation of olefins. MOF synthesis was attempted with all four compounds but was ultimately unsuccessful. Although one MOF was produced from Mo(TPM- 1)(CO)3, large scale synthesis was not possible preventing full investigation of its properties. iii Acknowledgments I would like to thank my doctoral supervisor Professor Datong Song for his guidance throughout the last few years. Also thanks to my internal committee members Professor Robert Morris and Professor Ulrich Fekl who provided invaluable direction and assistance. Lastly I would like to acknowledge my examination committee members, Professor Bernie Kraatz, Professor Jik Chin, and external examiner Professor Suning Wang, who provided insightful feedback for the final version of this thesis. Several people assisted with the work contained within this thesis. Thanks to Andrew Proppe of the Ted Sargent Group for quantum yield and luminescent lifetime measurements of [Cu9L6Br2][CuBr2]. My collaborators at the University of Calgary, Professor George Shimizu and Benjamin Gelfand, assisted with gas sorption measurements of [Ni(BPM)]n∙xDMSO. Our collaborators at the University of Ottawa, Professor Tom Woo and Hana Dureckova, contributed to computational modeling of [Ni(BPM)]n∙xDMSO. I also had the privilege of working with a stellar undergraduate student, Cindy Ma. After some initial guidance, Cindy seemed to make every metal acetate in our lab form a coordination polymer or MOF. Cindy was also able to deduce the correct procedure to synthesize [Ni(BPM)]n∙xDMSO which required an unintuitive trisolvent mixture. Following Cindy’s procedures Sheree Zhang and Michaela Deng helped make bulk samples of [Ni(BPM)]n∙xDMSO for characterization and gas sorption testing. Riley Choi aided further investigation into iron coordination polymers and Jingning Zhou cracked the synthesis for [Eu(BPM)(OAc)]n. Bulk synthesis of coordination polymers and MOFs synthesized from H2BPM (compounds 7-13) for characterization was conducted by Yujin Yamamotto and, again, Michaela Deng. Lastly, I would like to thank Quiming (Walter) Liang who worked tirelessly on synthesizing derivatives of Mo(TPM-1)CO3 (14) in an effort to make an isoreticular TPM MOF series. Walter’s work allowed for the synthesis of Mo(TPM-2)CO3 (15) and investigation of its catalytic properties. A special thanks to all the Song Group members past and present: Runyu Tan, Yu Li, Tao Bai, Shaolong Gong, Xiaofei Li, Kim Osten, Rhys Batcup, Tara Cho, Celia Gendron-Herndon, Adam Pantaleo, Yanxin Yang, Trevor Janes, Fred Chiu, Ellen Yan, and Daniel Dalessandro. You all livened up the lab. An extra special thanks to my undergraduate students, Cindy Ma and Walter Liang, and my other volunteer students who were wonderful to work with. iv No PhD can be successful without support from outside of the lab. Therefore, I would like to thank Anna Liza Villavelez (grad office), Ken Greaves (chem stores), John Ford (machine shop supervisor), Jack O’Donnell (glass shop), Ahmed Bobat (machine shop – creator of our MOF heating blocks), Darcy Burns (NMR facilities manager), Dmitry Pichugin (NMR facility), Rose Balazs (EA technician), Jack Jackiewicz (electronics shop), and Alan Lough (x-ray). It also takes a lot of effort to get into the grad program to begin with. To that end, a big thank you to Professor Tom Baker for allowing me the opportunity to work in your lab as an inexperienced second year undergrad at the University of Ottawa. Thank you to Dr. Daniel Harrison for being an amazing post-doc when I came back to Dr. Baker’s lab as a more experienced fourth year student. And thanks to Professor George Shimizu and Dr. Simon Iremonger who mentored me as a third year exchange student at the University of Calgary working in the wonderful world of MOFs. You all sparked my interest in MOFs and inspired me to make the leap to grad school. I also wouldn’t have been able to complete this doctorate without the support of my friends (both inside and outside the lab) and my family. I’m particularly proud, and thankful, that my papa, Edwin Kivi, will be around to see the first “Doctor Kivi” in the family. I will be able to answer “Yes!” when he asks if I’ve graduated yet! Thank you to my sister, Michelle, and brother in law, Richard Jagielowicz, for being there for me through thick and thin. Thank you to my parents for their love and support especially my mom, Catherine, for encouraging my interest in the natural world, and my father, Eric, for showing me how to think outside the box. Lastly, thanks to my special someone, Anneliese Neumann, for the long walks, companionship, and interesting lab book entries. v Table of Contents Acknowledgments.......................................................................................................................... iv Table of Contents ........................................................................................................................... vi List of Tables ...................................................................................................................................x List of Schemes ............................................................................................................................. xii List of Equations .......................................................................................................................... xiii List of Figures .............................................................................................................................. xiv List of Appendices ................................................................................................................... xxviii List of Abbreviations and Symbols............................................................................................ xxix Chapter 1 ..........................................................................................................................................1 1 Introduction .................................................................................................................................1 1.1 Introduction to Metal-Organic Frameworks ........................................................................1 1.1.1 Definition of a Metal-Organic Framework ..............................................................1 1.1.2 Early Examples of
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