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Synthesis, Characterization and Thermal Analysis Of SYNTHESIS, CHARACTERIZATION AND THERMAL ANALYSIS OF TETRAHEDRAL AND CYANO-SUBSTITUTED PERYLENE-BASED DERIVATIVES A Thesis Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Master of Science Ding Tian August, 2014 i SYNTHESIS, CHARACTERIZATION AND THERMAL ANALYSIS OF TETRAHEDRAL AND CYANO-SUBSTITUTED PERYLENE-BASED DERIVATIVES Ding Tian Thesis Approved: Accepted: _______________________________ _______________________________ Advisor Dean of the College Dr. Stephen Z. D. Cheng Dr. Stephen Z. D. Cheng _______________________________ _______________________________ Faculty Reader Dean of the Graduate School Dr. Mesfin Tsige Dr. George R. Newkome _______________________________ _______________________________ Department Chair Date Dr. Coleen Pugh ii ABSTRACT Perylene diimides (PDIs) have attracted the great interests of both academic and industrial people over decades of years because of their chemical stability, thermal stability, fluorescence, and photoactive property. They have been widely used as dyes, pigments, n-type organic semiconductors and organic field effect transistors (OFETs) and so on. However, in addition to molecular chemical nature, the self-assembly structure also deeply affected material’s macroscopic property and practical application. In order to get highly ordered assembly structure, we investigated the use of PDI-based derivatives as building blocks of supramolecular self-assembly and liquid crystals via modifying PDI’s imide position by alkyl chains and functional groups. Three tetrahedral PDI-based molecules tethering with different length of alkyl tails (decyl, dodecyl, tetradodecyl) and four cyano-substituted PDIs were successfully synthesized via a systematic and convenient method, getting rid of the low solubility of perylene. The chemical structures of products were fully characterized by proton nuclear magnetic resonance (1H NMR) spectroscopy and matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectroscopy. Their thermal stability could be maintained until 320 ℃ according to the results of thermogravimetric analysis (TGA). Differential scanning calorimetry (DSC) showed that the modified PDIs had the potential to form ordered structure by thermal annealing. iii ACKNOWLEDGEMENTS I would like to thank my advisor, Dr. Stephen Z. D. Cheng, to offer me this precious opportunity to learn and work in his excellent group. He always gave me great inspiration, guidance and encouragement for my research, and also valuable advice for my life. I would like to thank my faculty reader, Dr. Mesfin Tsige, who gave me lots of useful help on my thesis and presentation. I would like to thank my mentor Dr. Chih-Hao Hsu. He taught me how to do research from the beginning, and gave me a lot of help, guidance and inspiring talk throughout my research in the past two years. I would meet great difficulty without his support. I also would like to thank Dr. Kwang-Un Jeong, Mr. Mingjun Huang and all the other Dr. Cheng’s group members for their help on this project. Finally, I would like to thank my parents, family, and friends in China and in U.S. for their great support and love. iv TABLE OF CONTENTS Page LIST OF FIGURES ........................................................................................ vii LIST OF SCHEMES........................................................................................ ix CHAPTER I. INTRODUCTION ........................................................................................ 1 II. BACKGROUND ......................................................................................... 7 2.1 Perylene and Perylene Diimide (PDI).........................................................7 2.2 Introduction of Liquid Crystal (LCs) ................................................. 11 2.3 Introduction of Self-assembly ............................................................ 14 III. EXPERIMENTAL ................................................................................... 16 3.1 Chemicals and Solvents ..................................................................... 16 3.2 Molecular Characterizations .............................................................. 17 3.3 Synthetic Route of Modification Subunits ........................................ 20 3.4 Synthetic Route of Intermediate Molecule: Perylene-3,4-Anhydride-9,10- di-Decyloxycarbonyl................................................................................ 26 3.5 Synthetic Route of Tetrahedral Perylene-based Derivatives ............. 28 3.6 Synthetic Route of Cyano-substituted Perylene-based Derivatives .. 31 IV. RESULTS AND DISCUSSION ............................................................... 34 4.1 Synthetic Route of Modification Units .............................................. 34 4.2 Synthetic Route of Intermediate Molecule: Perylene-3,4-Anhydride-9,10- di-Decyloxycarbonyl ............................................................................... 40 v 4.3 Synthetic Route of Tetrahedral Perylene-based Derivatives ............. 43 4.4 Synthetic Route of Cyano-substituted Perylene-based Derivatives .. 48 4.5 Thermal Analysis ............................................................................... 52 V. CONCLUSIONS ....................................................................................... 60 REFERENCES .............................................................................................. 61 vi LIST OF FIGURES Figure Page 1.1 The molecular model of tetrahedral PDIs ................................................... 6 1.2 The molecular model of cyano-substituted PDIs ........................................ 6 2.1 (a) Chemical structure of perylene. (b) Exploded view of perylene ........... 7 2.2 Chemical structure of PTCDA .................................................................... 8 2.3 Macroscopic appearance of PTCDA .......................................................... 8 2.4 Electron distribution of CDA. ..................................................................... 9 2.5 Chemical structures of industrial PDI pigments ......................................... 9 2.6 Chemical structure of perylene diimide (PDI) .......................................... 10 2.7 Molecule packing models of solid, liquid crystal and liquid .................... 13 4.1 1H NMR spectra of (a) methyl 3,4,5-tridodecyloxybenzoate, (b) 3,4,5-tridodecyloxybenzylic alcohol, (c) 3,4,5-tridodecyloxybenzylbromide, (d) 3,4,5-tridodecyloxybenzylazide, (e) 3,4,5-tridodecyloxybenzylamine ..... 39 4.2 1H NMR spectra of (a) 3,4,5-tritetradecyloxybenzylamine， (b) 3,4,5-tridecyloxybenzylamine ................................................................... 40 4.3 1H NMR spectrum of PADE ..................................................................... 42 4.4 1H NMR spectra of (a) di-(decyloxycarbonyl)-perylene-1-(3,4,5)G12, (b) anhydride-perylene-1-(3,4,5)G12, (c) tetra-PDI-1-(3,4,5)G12 ................. 45 4.5 1H NMR spectra of (a) tetra-PDI-1-(3,4,5)G10, (b) tetra-PDI-1-(3,4,5)G14 .............................................................................. 46 4.6 MOLDI-TOF mass spectra of (a) tetra-PDI-1-(3,4,5)G12, (b) tetra-PDI-1-(3,4,5)G10, (c) tetra-PDI-1-(3,4,5)G14 ................................. 47 4.7 1H NMR spectra of (a) cyanobiphenyl-perylene-1-(3,4,5)G12, vii (b) cyanobiphenyl-perylene-1-(3,4,5)G14, (c) cyanophenyl-perylene-1-(3,4,5)G12, (d) cyanophenyl-perylene-1-(3,4,5)G14 ......................................................... 49 4.8 MOLDI-TOF mass spectra of (a) cyanobiphenyl-perylene-1-(3,4,5)G12, (b) cyanobiphenyl-perylene-1-(3,4,5)G14, (c) cyanophenyl-perylene-1-(3,4,5)G12, (d) cyanophenyl-perylene-1-(3,4,5)G14 ........................................................................................................................ 51 4.9 TGA curves of (a) tetra-PDI-1-(3,4,5)G12, (b) tetra-PDI-1-(3,4,5)G10, (c) tetra-PDI-1-(3,4,5)G14, (d) cyanobiphenyl-perylene-1-(3,4,5)G12, (e) cyanobiphenyl-perylene-1-(3,4,5)G14, (f) cyanophenyl-perylene-1-(3,4,5)G12, (g) cyanophenyl-perylene-1-(3,4,5)G14 ......................................................... 55 4.10 DSC curves of (a) cyanobiphenyl-perylene-1-(3,4,5)G12, (b) cyanobiphenyl-perylene-1-(3,4,5)G14, (c) cyanophenyl-perylene-1-(3,4,5)G12, (d) cyanophenyl-perylene-1-(3,4,5)G14 ........................................................................................................................ 59 viii LIST OF SCHEMES Scheme Page 4.1 Synthetic route of 3,4,5-trialkoxybenzylamine ........................................ 35 4.2 Synthetic route of PADE .......................................................................... 41 4.3 Synthetic route of tetrahedral PDIs .......................................................... 43 4.4 Synthetic route of cyano-substituted PDIs ............................................... 48 ix CHAPTER I INTRODUCTION Perylene is inexpensive, readily available, and robust compound.1 Many of its derivatives, such as perylene diimides (PDIs), have excellent electroactive properties and photoactive properties, and wonderful thermal, chemical and photochemical stability.2-5 PDIs have attracted great interest of scientists, and been under thoroughly study for lots of years. Not only because are they in an important class of n-type organic semiconductor with promising practical application, but also they can serve as intriguing building blocks for supramolecular self-assembly6 and
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