Syntheses and Characterization of Linearly Extended Tropylium Salts As N-Type Organic Semiconductors
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University of New Hampshire University of New Hampshire Scholars' Repository Master's Theses and Capstones Student Scholarship Fall 2015 SYNTHESES AND CHARACTERIZATION OF LINEARLY EXTENDED TROPYLIUM SALTS AS N-TYPE ORGANIC SEMICONDUCTORS Jinyu Yang University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/thesis Recommended Citation Yang, Jinyu, "SYNTHESES AND CHARACTERIZATION OF LINEARLY EXTENDED TROPYLIUM SALTS AS N- TYPE ORGANIC SEMICONDUCTORS" (2015). Master's Theses and Capstones. 1038. https://scholars.unh.edu/thesis/1038 This Thesis is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Master's Theses and Capstones by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. SYNTHESES AND CHARACTERIZATION OF LINEARLY EXTENDED TROPYLIUM SALTS AS N-TYPE ORGANIC SEMICONDUCTORS BY JINYU YANG B.S., Nanchang Hangkong University, 2012 THESIS Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Master of Science in Chemistry September, 2015 This thesis has been examined and approved in partial fulfillment of the requirements for the degree of Master in Chemistry by: Thesis Director, Glen P. Miller, Professor of Chemistry and Materials Science Arthur Greenberg, Professor of Chemistry Erik Berda, Associate Professor of Chemistry and Materials Science On June 26, 2015 Original approval signatures are on file with the University of New Hampshire Graduate School. ACKNOWLEDGEMENTS First and foremost, I would like to thank my father, De Yang and my mother, Xiuzhen Yan for their endless love, care and support. They were the guardians of the child, guides of the teenager and the advocates of the young man. I never feel afraid and lonely because I know they will always be by my side and supporting me no matter what happens. I would like to thank my advisor, Dr. Glen Miller for his help and support. He was always there to offer suggestions and guidance whenever there was a problem with the project. His encouragement always helped me get over of the frustration of failed experiments. From him I learned how to be a scientific researcher and writer. I would like to thank my committee members, Dr. Arthur Greenberg and Dr. Erik Berda for their help on my research and the time spent on reading my thesis. Their invaluable suggestions on my research lead to many interesting discoveries. I would also like to thank Dr. Charles Zercher, Dr. Richard Johnson, Dr. Sterling Tomellini and Dr. Samuel Pazicni for their enlightening lectures. They helped to set the foundation of my research. Last but not least, I cannot miss the chance to thank all Miller group members, especially Jianyu Zhao, Hao Geng, Yadi Wang and Yanmei Rong. They were always there to help and their company made the stressful graduate career easier. I would also like to thank all the professors and staffs of chemistry department who have helped me during my master study. iii TABLE OF CONTENTS ACKNOWLEDGEMENTS ........................................................................................................... iii LIST OF FIGURES ...................................................................................................................... vii LIST OF SCHEMES.................................................................................................................... viii LIST OF TABLES .......................................................................................................................... x LIST OF NUMBERED STRUCTRUES ....................................................................................... xi ABSTRACT ................................................................................................................................. xiii CHAPTER 1 INTRODUCTION .................................................................................................... 1 1.1 Origin of Organic Semiconductor Materials ......................................................................... 1 1.2 Classification of Organic Semiconductor Materials ............................................................. 2 1.2.1 Conjugated Polymers ...................................................................................................... 2 1.2.2 Small Molecules ............................................................................................................. 2 1.3 p-Type & n-Type Organic Semiconductors .......................................................................... 5 1.4 Application of Organic Semiconductors ............................................................................... 6 1.4.1 Organic Light-emitting Diodes (OLED) ........................................................................ 6 1.4.2 Organic Photovoltaic Devices (OPVs) ........................................................................... 7 1.5 Tropylium Ion Species as a Promising n-Type Organic Semiconductor Material ............... 9 CHAPTER 2 SYNTHESES AND CHARACTERIZATION....................................................... 10 2.1 Proposed Synthetic Route ................................................................................................... 10 2.2 Synthesis of Acenotropones ................................................................................................ 11 iv 2.2.1 Synthesis of Benzotropone ........................................................................................... 12 2.2.2 Synthesis of 2,7-Dimethyl-4,5-benzotropol ................................................................. 15 2.2.3 Synthesis of 4,6-Dimethyl-1,2-benzotropylium Tetrafluoroborate 8 ........................... 17 2.2.4 UV-Vis Spectroscopy Analysis of 8 ............................................................................. 19 2.2.5 Synthesis and UV-Vis Spectroscopy Analysis of 12.................................................... 21 2.2.6 Synthesis and UV-Vis Spectroscopy of 5-benzo-4,6-dimethyl-1,2-benzotropylium tetrafluoroborate 14 ............................................................................................................... 23 2.2.7 Synthesis of 4,6-Dimethyl-5-hydroxyl-1,2-acenotropylium Tetrafluoroborate 15 ...... 25 2.2.8 UV-Vis Spectroscopy Analysis of 15 ........................................................................... 26 2.2.9 Conclusion of Synthesis of Benzotropylium Tetrafluoroborates ................................. 27 2.3 Synthesis of 4,6-Dimethyl-1,2-naphthotropylium Tetrafluoroborate ................................. 28 2.3.1 UV-Vis Spectroscopy of 20 .......................................................................................... 30 2.3.2 Stability Study of 20 ..................................................................................................... 31 2.4 Synthesis of 4,6-Dimethyl-1,2-anthracenotropylium Tetrafluoroborate............................. 33 2.4.1 Synthesis of Anthracene-2,3-dicarboxaldehyde 21 ...................................................... 33 2.4.2 Synthesis of 24.............................................................................................................. 37 2.4.3 UV-Vis Study of 24 ...................................................................................................... 37 2.5 Chapter Conclusion ............................................................................................................. 38 CHAPTER 3 OTHER SYNTHESIZED COMPOUNDS ............................................................. 41 3.1 Synthesis of 2,3;6,7-Diepoxy-2,7-dimethyl-4,5-benzotropone ........................................... 41 v 3.2.1 A New Strategy Synthesis of Substituted Acenes ........................................................ 42 3.2.2 Proposed Mechanism for the Formation of 29 and 30 ................................................. 44 CHAPTER 4 EXPERIMENTAL SECTION ................................................................................ 46 4.1 General Methods ................................................................................................................. 46 4.2 Solvents ............................................................................................................................... 47 4.3 Reagent ................................................................................................................................ 48 4.4 Syntheses ............................................................................................................................. 50 APPENDIX ................................................................................................................................... 66 vi LIST OF FIGURES Figure 1. Polyacetylene. .................................................................................................................. 1 Figure 2. Polypyrrole (left) and Polythiophene (right). .................................................................. 2 Figure 3. Pentacene (left) and Bis(phenylthio)pentacene (right). ................................................... 4 Figure 4. α,ω-Dihexyl-substituted sexithiophene. .......................................................................... 5 Figure 5. Fullerene. ......................................................................................................................... 6 Figure