Synthesis and Functionalization of Three-Dimensional Covalent Organic Frameworks by Xingjian Ma A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Chemical Engineering) in The University of Michigan 2019 Doctoral Committee: Associate Professor Timothy F. Scott, Chair Professor Brian J. Love Associate Professor Sunitha Nagrath Professor Robert M. Ziff Xingjian Ma [email protected] ORCID ID: 0000-0001-9454-4065 © Xingjian Ma 2019 DEDICATION This dissertation is dedicated to Mom and Dad Xinyi For their endless love and support ii ACKNOWLEDGEMENTS First, I would like to thank my PhD advisor Professor Timothy F. Scott, for his constant guidance, support, and encouragement throughout my doctoral studies at the University of Michigan. I am especially thankful for his understanding of my foray into consulting and his patience with all the research difficulties I have encountered. I would also like to express my gratitude to my dissertation committee members, Professor Sunitha Nagrath, Professor Robert Ziff and Professor Brian Love for their constructive feedback for my project. I must emphasize how lucky I am to have extremely supportive and encouraging lab mates including Dr. Scott Zavada, Dr. Joseph Furgal, Dr. Tao Wei, Dr. Dowon Ahn, Dr. Megan Dunn, Dr. Harry van der Laan, Samuel Leguizamon, Abdulla Alqubati, Austin Bingham, Alex Commisso, Futianyi Wang, Dr. Jae Hwan Jung, Dr. Junting Li, Sameer Sathe, Dan Li, Nathan Wood, and Aishwarya Chandrashekar. I want to thank them for building the family atmosphere of our Polymer Dojo and I really appreciate their camaraderie and friendship over these last five years. I am especially appreciative of the mentorship from Scott, Tao, and Megan during my early years in the group, and for their invaluable advice on research and life. I would also like to mention Harry and Alex for maintaining a safe lab environment and Sam and Abdulla for their efforts towards ensuring smooth daily operation and cleanliness of our lab. I have had the fortune of working with two excellent undergraduate researchers, Sari B. Goldstein and Kristin Lewis, who assisted me with many tasks associated with my research. I want to mention Sari specifically for helping me with hundreds of scandium triflate COF synthesis trials that ultimately led to a breakthrough. iii I want to thank my fellow Chemical Engineering graduate students who have assisted me with the various instruments I have needed during my studies, including Doug Montjoy, who helped me with scanning electron microscopy (SEM), and Jiwoong Kang, Zixuan Wang, and Xiaowen Zhao for helping me with BET surface area measurements. I would also like to thank Dr. Daniel Holmes from the Chemistry Department at Michigan State University for running Solid-state Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS 13C NMR) on my samples. I am also grateful for the staff members of the Chemical Engineering department, particularly Susan Hamlin, Barbara Perry, Kelly Raickovich, Jennifer Downey, and Shelley Fellers for their assistance with chemical purchases and many other things. I have had the fortune of befriending some amazing individuals during my time at Michigan. Tingwen Lo, Tianhui Ma, Yufei Wei, and Xiaowen Zhao were all in my Chemical Engineering cohort, and their companionship have been invaluable these last five years, and I am glad Yufei and Xiaowen will be in Indianapolis with me as I embark on a new adventure. In addition, I am deeply grateful to have met my dearest friends Jiji Ahn, Jonathan Bezenah, Chansoo Lee, Kristina Oberly, and Rohan Jalalizadeh, who started out as a board game group but have evolved into a second family that has been an instrumental source of motivation and support. I must express my eternal gratitude to my parents, for their endless love, understanding, and support of all my decisions and endeavors. I am also thankful for having my sister, Xinyi, live with me for the past three years and help me create a slice of home on the other side of the world in Ann Arbor. iv TABLE OF CONTENTS DEDICATION .............................................................................................................. ii ACKNOWLEDGEMENTS ......................................................................................... iii LIST OF FIGURES ................................................................................................... viii LIST OF SCHEMES ................................................................................................ xvii LIST OF TABLES ..................................................................................................... xxi ABSTRACT ............................................................................................................. xxiii Chapter 1 Introduction ................................................................................................. 1 1.1 Original Publication Information .................................................................................. 1 1.2 Covalent Organic Frameworks ...................................................................................... 1 1.3 Two-dimensional versus Three-dimensional COFs ....................................................... 3 1.4 3D COF Linkages ........................................................................................................... 4 1.4.1 Boron-oxygen Linkages ............................................................................................ 5 1.4.2 Imine Linkages ....................................................................................................... 10 1.4.3 Other Linkages ....................................................................................................... 18 1.5 Functionalization and Modification of 3D COFs ......................................................... 21 1.6 Challenges in 3D COF Development ............................................................................ 25 1.6.1 Disparity between 2D and 3D Frameworks ............................................................. 25 1.6.2 Addressing the Crystallization Problem .................................................................. 25 1.6.3 Deficient Systematic Understanding ....................................................................... 30 1.6.4 Limited Topologies and Building Blocks ................................................................ 32 1.6.5 Controlling Network Interpenetration ..................................................................... 33 1.7 Overview of Subsequent Chapters ............................................................................... 34 1.8 References ..................................................................................................................... 36 Chapter 2 Synthesis of Tetrahedral Monomers and Imine-linked 3D COFs ........... 46 v 2.1 Abstract ......................................................................................................................... 46 2.2 Introduction .................................................................................................................. 46 2.3 Experimental................................................................................................................. 48 2.3.1 General Experimental Procedure ............................................................................. 48 2.3.2 Monomer Synthesis ................................................................................................ 49 2.3.3 Imine-linked 3D COF Synthesis ............................................................................. 63 2.4 Results and Discussion .................................................................................................. 66 2.4.1 Monomer Synthesis ................................................................................................ 66 2.4.2 COF-300 Synthesis and Characterization ................................................................ 68 2.4.3 COF-320 Synthesis and Characterization ................................................................ 74 2.4.4 Tetraamine-tetraaldehyde COF Synthesis and Characterization ............................... 77 2.5 Conclusions ................................................................................................................... 78 2.6 References ..................................................................................................................... 79 Chapter 3 Low Temperature Synthesis of Imine-linked 3D COFs Utilizing Scandium Triflate ..................................................................................................................................... 81 3.1 Abstract ......................................................................................................................... 81 3.2 Introduction .................................................................................................................. 82 3.3 Experimental................................................................................................................. 84 3.3.1 General Experimental Procedure ............................................................................. 84 3.3.2 Solvothermal Synthesis of COF-300 ....................................................................... 85 3.3.3 In-situ Deprotection and Synthesis of COF-300 ...................................................... 86 3.3.4 Scandium Triflate Catalyzed