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Carboxy Fantrip Monomer Was Used in the Langmuir-Blodgett Synthesis of Poly(Carboxyfantrip)

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Carboxy Fantrip Monomer Was Used in the Langmuir-Blodgett Synthesis of Poly(Carboxyfantrip) University of Nevada, Reno The Synthesis and Fabrication of Two-Dimensional Polymers A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry by William Bailey Thompson Dr. Benjamin T. King/Dissertation Advisor May 2019 THE GRADUATE SCHOOL We recommend that the dissertation prepared under our supervision by William Bailey Thompson Entitled The Synthesis and Fabrication of Two-Dimensional Polymers be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Benjamin T. King , Advisor Christopher S. Jeffrey , Committee Member Robert S. Sheridan , Committee Member Lora Robinson , Committee Member Jonathan Weinstein , Graduate School Representative David W. Zeh, Ph.D., Dean, Graduate School May-2019 i Abstract The Synthesis and Fabrication of Two-Dimensional Polymers William Bailey Thompson Ph.D Advisor: Professor Benjamin T. King With the isolation of graphene, there has been a proverbial gold rush in the field of two- dimensional (2D) materials because their unique properties promise numerous applications. The synthesis of 2D materials is currently a hot field with many branches, one of them being synthetic two-dimensional polymers (2DPs). 2DPs share many similarities with other 2D materials but promise tunable properties for various applications. This dissertation focuses on the synthesis and use of monomers that can be fabricated into 2DPs by crystallization or Langmuir-Blodgett approach. Chapter One will explore how 2DPs are classified and showcase some of the current methods for the synthesis of 2DPs. The pros and cons of each method will be highlighted and potential applications of 2DPs will be discussed. Chapter Two describes the synthesis of the monomers fantrip and carboxyfantrip. The fantrip monomer was used in the crystalline-state synthesis of poly(fantrip) and the carboxy fantrip monomer was used in the Langmuir-Blodgett synthesis of poly(carboxyfantrip). The chapter also describes optimization of their syntheses. Chapter Three focuses on the fabrication of poly(carboxy fantrip) by Langmuir-Blodgett techniques. The chapter contains a brief theory behind Langmuir-Blodgett and characterization ii techniques used on 2DP films. Past and current challenges of using poly(carboxy fantrip) are also present in the chapter. Chapter 4 contains different gas flow measurement through poly (carboxy fantrip). The chapter focuses on using fabricated film for gas flow studies and explains challenges occurred in obtain gas flow data for poly(carboxy fantrip). iii This thesis is dedicated: To my friends and family for their love and support. iv Acknowledgements I would like to thank my parents and family for their support throughout the years. They have done so much for me over the years that I might not ever be able to repay their kindness, but I will try my hardest to find a way. I would like to thank my advisor Benjamin T. King for the opportunity to work on a variety of novel projects and introducing me to the wider world of chemistry. I would like to thank the entire chemistry department at UNR, faculty and students for all the good memories and the camaraderie. There are just too many people to name on here. I would like to thank the entire King group, past and present. There may never be a better group of people to work with ever again. Special thanks to Dustin, Daniel, Jonathan, Carey, Devin, Manuel, Drew. The memories from this lab will last a lifetime. A special shout out to Devin Grainer who helped me improve this dissertation with his extensive chemistry knowledge and better grammar. A special shout out to Dr. Patterson (Dustin) for all the time talking about chemistry and life. Also, for helping me to improve my golf game. v Table of Contents Chapter 1……………………………………………………………………………….………...1 1.1. Two-Dimensional Polymers and Fantrip…………………………………………………….1 1.2. Two-Dimensional Polymers…………………………………………………………………5 1.3. Possible Applications of 2D-Polymers…………………………………………………..…..9 1.4. Synthesizing 2DPs……………………………………………………………………….....12 1.5. Solid Surface Approach to 2DPs ……………………………………………………..……16 1.6. Solution Phase Approach…………………………………………………………………...17 1.7. Air-Water Interface Approach………………………………………………………….…..20 1.8. Precursor to Fantrip Monomer Synthesis……………………………………………….…..22 1.9. References………………………………………………………………………………….28 Chapter 2: Synthesis of Carboxy Fantrip…………………………………………………....…..31 2.1 Past Monomers for 2DP………………………………………………………………..…….31 2.2 Synthetic Route Towards Fantrip……………………………………………….……………33 2.3 Starting Synthesis of Carboxy Fantrip………………………………………………………..38 2.4 Different Methods for Cheletropic Eliminations………………………………………….….50 2.5 Lithium Reagents for Benzyne Formation……………………………………………….…..56 2.6 Carboxylic Acid Protection…………………………………………………………..………60 2.7 Rearrangement of Triptycene Core………………………………………………….……….65 2.8 Reactivity of the Monomers…………………………………………………………….……67 vi 2.9 Conclusion……………………………………………………………………………………70 2.10 Experimental Section………………………………………………………..………..…….71 2.11 References………………………………………………………………………..…….….107 Chapter 3 Fabrication of Poly (carboxy fantrip) Films…………………………………..……..110 3.1 Langmuir Films…………………………………………………………………….…….…110 3.2.1 Parts of the Langmuir-Blodgett Trough…………………………………...……….……..114 3.2.2 Solubility of Compounds……………………….…………………………………..…….116 3.3 Causes of Defects in Film…………………………………………………………………..118 3.4.1 Transferring Langmuir Films……………………………………………………....……..119 3.4.2 Horizontal Deposition……………………………….………………………………..…..121 3.5 Langmuir-Shäfer (Horizontal Transfer)………………………………………………...…..122 3.5 Substrate Functionalization……………………………………………..…………….…….122 3.6 Brewster Angle Microscopy (BAM)……..……………………………………………..….125 3.7 Optical Microscopy………………..………………………………….………………….…127 3.8 Scanning Electron Microscope (SEM)………………………..……………………………129 3.9 Poly(carboxy fantrip) Films………………………………………………………..……….129 3.10 Defects in poly (carboxy fantrip)………………………………………………………….138 3.12 Stability of Poly (carboxy fantrip) Film…………………………………………………...145 vii 3.13 Roughness of Substrates…………………………………………………………………...152 3.14 Conclusion………………………………………………………………………………....155 3.15 Experimental…………………………………………………………………………...….156 3.16 References……………………………………………………………………………...….160 Chapter 4: Poly (carboxy fantrip) Gas Flow……………………………………………....…...163 4.1 Gas Flow Through Membranes…………………………………………………………..…163 4.2 Gas Flow Through poly (carboxy fantrip)……………………………………………….…165 4.3 Conclusion…………………………………………………………………………………..169 4.4 Experimental………………………………………………………………………………..170 4.5 References……………………………………………………………………………..……172 viii Chapter 1 List of Figures Figure 1.1 Three different 1-dimensional polymer architectures……………………….…………2 Figure 1.2 Different topologies of polymers types………………………………………….……..3 Figure 1.3 A section of molecular structure of graphene, the archetypal 2D polymer…………....4 Figure 1.4 Example of poly(styrene) and poly(styrene-butadiene-styrene)……………….………6 Figure 1.5 A tiling set where a single tile being used to cover a plane…………………….……...7 Figure 1.6 In tiling there is three sets of tiles that can be described……………………….………8 Figure 1.7 A couple of possible monomer configuration………………………………….………8 Figure 1.8 Müller and co-workers monomer used to make their 2DP……………….…….……..10 Figure 1.9 An illustration of a monolayer membrane…………………………………….………11 Figure 1.10 Monomer synthesized to make the 2DP after crystallization………………….…….14 Figure 1.11 Monomer synthesized and crystalized and polymerize to form the crystals…….…..15 Figure 1.12 Structure of antrip monomer………………………………………………….……..16 Figure 1.13 Using Ullman reactions on the surface of copper produced sheets…………….……17 Figure 1.14 Triptycene core monomer was used in the synthesis of their 2DP in solution….…..19 Figure 1.15 Bai and co-workers synthesis a set of monomers when put into solution…….……..20 Figure 1.16 A terpyridine monomer unit placed on the air/water interface………………….…...22 Figure 1.17 Resonance structures of anthracene…………………………………………….……22 Figure 1.18 [4+4] cycloaddition of anthracene……………………………………………….…..22 Figure 1.19 The reactive anthracene blades attached to the antrip molecule……………….……23 Figure 1.20 The free bond rotation of Fridel Craft reaction………………………………….…..24 Figure 1.21 Antrip’s example of a regioisomer with bond rotation………………………….…..25 Figure 1.22 The less stable isoindole moiety and the fluoro substituted isoindole……….……...26 Figure 1.23 The different stackings of molecules based on their electronics……………….……27 ix Chapter 2 List of Figures Figure 2.1 Antrip monomer and fantrip monomer………………………………………………..31 Figure 2.2 The monomer antrip-DEG and hydroxy fantrip……………………………………….32 Figure 2.3 HRMS of fantrip trifold with multiple stages of chelotropic elimination…………….37 Figure 2.5 TOF-HRMS of an impure sample of hexabromo triptycene carboxylic acid…………43 Figure 2.5 Crystal structure of carboxy HBT grown in THF……………….……………………43 Figure 2.6 DSC of carboxy HBT and TGA of carboxy HBT…………………………………….44 Figure 2.7 Possible bi-products of the three-fold benzyne reaction………………………………46 Figure 2.8 Carboxy trifold different byproducts after column chromatography………………….47 Figure 2.9 Cheletropic elimination into carboxyfantrip using hydrogen peroxide……………….48 Figure 2.10 Crude after cheletropic elimination with hydrogen peroxide…….………………….49 Figure 2.11 Crystal structure of carboxy fantrip using 1,4-dioxane as a cocrystal………………50 Figure 2.12 Cheletropic elimination of the N-methyl bridge by Gribble…………………………51 Figure
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