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Hydroboration of Conjugated Materials: Applications of NHC-Cu(I) Catalysis Emily Montgomery

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Hydroboration of Conjugated Materials: Applications of NHC-Cu(I) Catalysis Emily Montgomery Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2012 Hydroboration of Conjugated Materials: Applications of NHC-Cu(I) Catalysis Emily Montgomery Follow this and additional works at the FSU Digital Library. For more information, please contact [email protected] THE FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES HYDROBORATION OF CONJUGATED MATERIALS: APPLICATIONS OF NHC-CU(I) CATALYSIS By EMILY MONTGOMERY A Thesis submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Master of Science Degree Awarded Fall Semester, 2012 11111111 i Emily Montgomery defended this thesis on November 7, 2012. The members of the supervisory committee were: Major Professor; D. Tyler McQuade Professor Directing Thesis Committee Member; Geoff Strouse Committee Member Committee Member; Michael Shatruk Committee Member The Graduate School has verified and approved the above-named committee members, and certifies that the thesis has been approved in accordance with university requirements. ii The views expressed in this article are those of the author and do not reflect the official policy or position of the United States Air Force, Department of Defense, or the U.S. Government iii ACKNOWLEDGEMENTS I would like to acknowledge Dr. Tyler McQuade and the McQuade Research lab for allowing me to join the group and providing me with an excellent learning environment. I would like to particularly thank Brian Ondrusek, Dr. Suzanne Opalka, Dr. Tania Houjeiry and Dr. Jin Kyoon Park for their contributions, mentorship and support. Special thanks to Brian Ondrusek, Dr Opalka and Dr McQuade for their help in editing this manuscript. I also wish to acknowledge the Air Force Institute of Technology and Air Force ROTC detachment at FSU for their funding and support they have provided. iv TABLE OF CONTENTS LIST OF FIGURES .................................................................................................................................. VI ABSTRACT ........................................................................................................................................... VII PART I CONJUGATED POLYMERS .............................................................................................. 1 1.1 Overview and Hydroboration Chemistry in the McQuade Group ............................................................... 1 1.2 Applications and Goals ..................................................................................................................................... 2 1.3 Monomer Synthesis ........................................................................................................................................... 4 1.4 Polymer Synthesis and Purification ................................................................................................................ 4 1.5 Hydroboration-oxidation of the Polymer ........................................................................................................ 5 1.6 Small Model System .......................................................................................................................................... 8 1.7 Conclusions ....................................................................................................................................................... 10 PART II POLYCYCLIC AROMATIC HYDROCARBONS ................................................................ 12 2.1 Overview and The Mallory Reaction ............................................................................................................. 12 2.2 An Even Simpler Model .................................................................................................................................. 15 2.3 Kinetics .............................................................................................................................................................. 17 2.4 Applications ...................................................................................................................................................... 18 2.5 Conclusions ....................................................................................................................................................... 21 APPENDIX A PART I SUPPORTING INFORMATION ................................................................. 22 APPENDIX B PART II SUPPORTING INFORMATION ............................................................... 34 BIOGRAPHICAL SKETCH ................................................................................................................. 39 BIBLIOGRAPHY .................................................................................................................................. 40 v LIST OF FIGURES Figure 1. Generic Conjugated Polymers ........................................................................................1 Figure 2. Precatalysts .....................................................................................................................1 Figure 3. Regioselective Hydroboration of Propargylic Alcohols/Ethers .....................................2 Figure 4. Sensor Response to Analyte ...........................................................................................2 Figure 5. Goal of the PPE System ..................................................................................................3 Figure 6. Monomer Synthesis ........................................................................................................4 Figure 7. Pd-catalyzed Polymerization ..........................................................................................4 Figure 8. Hydroboration (PPE-B) and Oxidation (PPE-C) of Polymer .......................................5 Figure 9a. 50 mol % Hydroborated Polymer .................................................................................6 Figure 9b. Fluorescence Spectrum of PPE-A and PPE-B ............................................................6 Figure 10a. Fluorescence Spectrum of PPE-A, PPE-B and PPE-C .............................................7 Fiugre 10b. Fluorescence of PPE-C Upon KOtBu Titration .........................................................7 Figure 11. Proposed Use of PPE-A as a Hydroboration Sensor ...................................................8 Figure 12. Model Compound Hydroboration ................................................................................8 Figure 13. MC-1A and Mixture of Hydroboration Isomers ..........................................................9 Figure 14. 1H NMR data for 6-NHC and 5-NHC-catalyzed Hydroboration Products ..................9 Figure 15. Model Compounds .....................................................................................................10 Figure 16. Vinyl Boronate Ester Substrate Under Investigation .................................................12 Figure 17. Photocyclization of Stilbene ........................................................................................13 Figure 18. Proposed Photocyclization to 9 ..................................................................................14 Figure 19. Hydroboration and Photocyclization of MC-2A ........................................................15 Figure 20. Rate Plot from GC Reaction Analysis ........................................................................16 Figure 21. Proposed Saccharide Sensor Model ...........................................................................18 Figure 22. A Shinkai-type Glucose Sensor ..................................................................................19 Figure 23. Two-point Glucose Sensor .........................................................................................19 Figure 24. Suzuki Coupling of 9 to Make OLED Compound 13 ................................................20 Figure 25. Suggested Synthetic Route to Graphitic Sheets .........................................................21 vi ABSTRACT This thesis presents the synthesis of a polyphenylenethynylene and subsequent photophysical characterization after post-polymerization treatments. The polymer fluorescence was quenched upon fractional hydroboration. To help better understand the observed changes, small molecule model compounds were also prepared and characterized. The novel structure and photochemistry of one of the model compounds inspired us to develop a new set of boronic ester chromogenic building blocks. The buiding blocks not only offer insight into applications of the original polymer system, but also are novel materials. vii CHAPTER I CONJUGATED POLYMERS 1.1 Overview and Hydroboration Chemistry in the McQuade Group Conjugated polymers (CPs) offer an advantage as organic semiconductors over their inorganic counterparts because of their low production cost and facile processing, and plastic properties that enable the development of mechanically flexible devices. Figure 1 features two representative examples of conjugated polymers.1 Enhancing existing conjugated polymer classes through post-polymerization functionalization is one strategy to introduce sensing capabilities or handles for further modification. We are particularly interested in using recently developed copper(I) catalysts to perform modification of polymers such as polyphenyleneethynylenes (PPEs). R R n n R R poly(p-phenylene vinylene)s poly(p-phenylene ethynylene)s PPVs PPEs Figure
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