Wilfrid Laurier University Scholars Commons @ Laurier Theses and Dissertations (Comprehensive) 2010 Microporous Organic Polymers: Synthesis and Post Synthetic Modifications Phillip Andrew Kerneghan Wilfrid Laurier University Follow this and additional works at: https://scholars.wlu.ca/etd Part of the Organic Chemistry Commons, and the Polymer Chemistry Commons Recommended Citation Kerneghan, Phillip Andrew, "Microporous Organic Polymers: Synthesis and Post Synthetic Modifications" (2010). Theses and Dissertations (Comprehensive). 985. https://scholars.wlu.ca/etd/985 This Thesis is brought to you for free and open access by Scholars Commons @ Laurier. It has been accepted for inclusion in Theses and Dissertations (Comprehensive) by an authorized administrator of Scholars Commons @ Laurier. For more information, please contact [email protected]. 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While these forms may be included Bien que ces formulaires aient inclus dans in the document page count, their la pagination, il n'y aura aucun contenu removal does not represent any loss manquant. of content from the thesis. 1+1 Canada Microporous Organic Polymers: Synthesis and Post Synthetic Modifications By Phillip Andrew Kerneghan BBSc, Wilfrid Laurier University, 2008 THESIS presented to The Faculty of Science, Department of Chemistry in partial fulfillment of the requirements for the degree of Master of Science in Chemistry Wilfrid Laurier University 2010 © Phillip Andrew Kerneghan 2010 AUTHOR'S DECLARATION I hereby declare that I am the sole author of this thesis. This is a true copy of the thesis, including any required final revisions, as accepted by my examiners. I understand that my thesis may be made electronically available to the public. Phil Kerneghan 1 Abstract Microporous solids are an important class of materials that have been studied extensively. Newer to this field are Microporous Organic Polymers (MOPs) which are networks constructed from smaller organic building blocks and exhibit large surface areas, small pore sizes and low densities. It is due to these characteristics that MOPs have attracted attention because of their potential use in applications such as catalysis, chemical separations and gas storage. In this thesis is described the synthesis of two novel MOPs, the first of which being a network based on benzenediboronic acid and triptycene building blocks linked together by boronate esters. This network showed a relatively low surface area of 200 m g" and guest uptake capacities of 18 % by mass. However, this network proved to be chemically unstable and the boronate ester linkages degrading when exposed to air. The second network was formed via Yamamoto coupling conditions and was based on tetraphenylbimesityl monomers. This network also showed a guest solvent uptake capacity of 18 % by mass while maintaining thermal stability up to 400 °C. The network also showed a relatively large surface area of 1424 m g" . In addition to synthesizing novel frameworks it was also possible to post synthetically modify two additional networks. The first post synthetic modications to a purely organic microporous material were performed on a network originally linked by imine bonds. First, the imine bonds within the network were reduced to amine bonds resulting in the network becoming more resistant to hydrolysis. However, because the rigid imine bonds were reduced, the network was allowed to collapse and permanent ii microporosity was lost. The amine bonds within the network were then acetylated in order to demonstrate that further post synthetic modifications were possible. The second network that we performed post synthetic modifications on was a Porous Aromatic Framework (PAF) comprised of tetraphenylmethane monomers. This network was brominated via electrophilic aromatic substitution to the phenyl rings present within the network. Modifications to this network resulted in a decrease in 9 1 9 1 surface area from 2250 m g" to 694 m g" and solvent guest uptake capacity from 28 % by mass to 16 % by mass. iii Acknowledgements I would first like to thank my mom, Maribeth, and dad, David, for all of their never ending love and support, financial included. Mom, thank you for all of your fantastic guidance and weekly phone conversations that often kept me on track. I couldn't have done it without your support. Dad, thanks for coming home everyday and telling me "Phillip, don't ever be an accountant!" I'm sure he's watching and approves of chemistry. I would also like to extend a special thank you to my supervisor Ken Maly for taking me in as his first Masters student. I especially appreciate your humour, kindness and friendship that made my time as an MSc student very enjoyable. I couldn't have survived with any supervisor other than you. I would also like to thank all of the peers whom I worked with in Ken's lab: Lynett, Shira, Marc, Andrew, Melissa, Caitlin, Katie, Tyler, Colin, Josh and Joe. We definitely had a lot of fun and made work never seem like work. Thank you to Professor David Bryce from the University of Ottawa for all of your assistance in running solid state NMR's for me and thank you to Dr's John Ripmiester and Steven Lang for inviting me to the NRC-SIMS and teaching me about gas adsorption. Funding for this thesis was provided NSERC and Wilfrid Laurier University. IV Table of Contents AUTHOR'S DECLARATION i Abstract ii Acknowledgements iv Table of Contents v List of Figures vi List of Schemes viii Abbreviations ix Chapter 1: Introduction 1 1.1 Microporous Materials 1 1.2 Metal Organic Frameworks 3 1.3 Polymers of Intrinsic Microporosity 5 1.4 Microporous Organic Polymers 7 1.5 Post Synthetic Modifications of Microporous Materials 11 1.6 Research Objectives 13 Chapter 2: Novel Triptycene Based Framework 15 2.1 Introduction 15 2.2 Synthesis 18 2.3 Results and Discussion 21 2.4 Summary 25 Chapter 3: Post Synthetic Modifications to an Imine Linked MOP 26 3.1 Introduction 26 3.2 Model Studies 27 3.3 Synthesis 29 3.4 Characterization of Networks 31 3.5 Summary 41 Chapter 4: Synthesis and PSM to Porous Aromatic Frameworks (PAFs) 42 4.1 Introduction of Tetraphenylmethane based PAFs 42 4.2 Synthesis and Characterization of Tetraphenylmethane based PAFs 43 4.2 Discussion of Tetraphenylmethane based PAFs 48 4.3 Bimesityl PAF Introduction 50 4.4 Synthesis of Bimesityl PAF 50 4.5 Characterization of Bimesityl PAF 52 4.6 Summary 55 Chapter 5: Conclusions and Future Work 56 Chapter 6: Experimental 58 6.1 General 58 6.1.1 Infrared Spectroscopy 58 6.1.2 NMR Spectroscopy 58 6.1.3 Elemental Analysis 58 6.1.4 Carbon-13 CP/MASNMR spectroscopy 58 6.1.5 Gas Adsorption Studies 59 6.1.6 Thermogravimetric Analysis 60 6.2 Synthesis 60 Chapter 7: References 75 v List of Figures Figure 1-1: General schematic showing the linking of polytopic building blocks to form synthetic networks 2 Figure l-2a: Representative formation of a Metal Organic Framework 4 Figure l-2b: Crystal structure of MOF-5 4 Figure 1-3: A general scheme illustrating the concept of post synthetic modifications to a porous framework 12 Figure 1-4: Scheme of representative post synthetic modification to IRMOF-3 with various anhydrides 12 Figure 2-1: IR spectum of model compound 5 20 Figure 2-2: IR spectrum of Triptycene MOP 22 Figure 2-3: Nitrogen isotherm plot of Triptycene MOP 23 Figure 2-4: Thermogravimetric analysis of Triptycene MOP 24 Figure 3-1: Infrared spectra of model compounds 28 Figure 3-2: Infrared spectra of Imine MOP, Reduced MOP, Amide MOP 32 Figure 3-3: 13C CP-MAS spectra of Imine MOP, Reduced MOP, Amide MOP 33 Figure 3-4: TGA traces of Imine MOP with THF, activated, and resolvated with THF 34 Figure 3-5: Nitrogen adsorption isotherm for Imine MOP and Reduced MOP 35 Figure 3-6: TGA traces of Reduced MOP with THF, activated, and resolvated with THF 37 Figure 3-7: Infrared spectrum of Reduced MOP after being subjected