此論文報道了作為有機半導體的一系列氮雜並五苯的理論計算，以及既可能作為有機半導體又能形成晶格包合物的萘基並四苯衍生物。第一章介紹了有機半導體和有機薄膜晶體管，並侧重于有機半導體的理论计算及基於有機薄膜晶體管的传感器。 根據基於B3LYP/6-311++g(d,p)//6-31g(d,p)基組的密度泛函理論計算，第二章討論了作為有機半導體的一系列氮雜並五苯的“結構-性能關系，特別是氮原子的數量、价态以及位置對一系列矽基乙炔基取代的氮雜並五苯的電子結構影響，包括前線分子軌道能級、電離能、電子親和勢以及重組能。对五個分子载流子遷移率的計算显示,當一個分子的最高位占據分子軌道能量高於一個閾值或者最低未占據分子軌道低於一個閾值時，空穴或電子遷移率的計算結果與實驗結果互相吻合。基於之前對5-(1’-萘基)並四苯的研究，第三章介紹了取代的5-(1’-萘基)並四苯的合成與晶格包合物。母分子萘基並四苯是一個有機半導體材料並且能夠在晶格中包合客体分子，這倆個性質使該分子在基于薄膜晶體管的蒸汽传感器中有潛在應用。為了增強包含客體分子的選擇性，我設計了一些取代的萘基並四苯,并成功合成了其中的四個。我測試了與客體分子形成晶格包合物的能力，並通過1H NMR和X射線衍射研究了晶格包合物的組成和結構。 / Reported in this thesis is a computational study on a series of organic semiconductors based on N-Heteropentacenes and a preliminary experimental study on substituted naphthyl-tetracenes, which are potential organic semiconductors with ability to trap guest molecules in the crystal lattice. Chapter 1 introduces organic semiconductors and organic thin film transistors (OTFTs) with emphasis on computational studies of organic semiconductors and chemical sensors based on OTFTs. On the basis of density function theory (DFT) calculation at the B3LYP/6-311++g(d,p)//6-31g(d,p) level of theory, Chapter 2 discusses the structure-property relationship for organic semiconductors of silylethynylated N-Heteropentacenes, particularly on how the number, degree of unsaturation and position of N atoms affect electronic structures of these silylethynylated N-Heteropentacenes, including frontier molecular energy levels, ionization potential, electron affinity and reorganization energies. The charge carrier mobilities for five molecules were calculated. The calculated hole or electron mobility is in agreement with the experimental values when the concerned molecule has its HOMO energy level higher than a threshold or LUMO energy level lower than a threshold, respectively. Such threshold effect is related to effective charge injection from metal electrode. Chapter 3 introduces synthesis and clathrates of substituted 5-(1’-naphthyl)tetracene (NT) on the basis of previous study on 5-(1’-naphthyl)tetracene (NT). Unsubstituted NT is an organic semiconductor that can trap guest molecules in its crystal lattice, and thus is of interests for chemical vapor sensing based on organic thin film transistors. To enhance the selectivity in including guest molecules, several substituted naphthyltetracenes were designed. Four of them were synthesized, tested in forming clathrates with several guest molecules. The compositions and structures of the resulting clathrates were studied with 1H NMR and X-Ray crystallography. / Detailed summary in vernacular field only. / Mao, Renxin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references. / Abstracts also in Chinese. / ABSTRACT --- p.i / 摘要 --- p.iii / Acknowledgement --- p.iv / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Organic Semiconductors and Organic Thin Film Transistors (OTFTs) --- p.1 / Chapter 1.2 --- Computational Study on Organic Semiconductors --- p.5 / Chapter 1.3 --- Chemical Vapor Sensors based on OTFTs --- p.13 / Reference --- p.18 / Chapter Chapter 2 --- Organic Semiconductors From N-Heteropentacenes: A Computational Study --- p.21 / Chapter 2.1 --- Introduction --- p.21 / Chapter 2.1.1 --- Theory and Tool for Calculating Charge Transport --- p.21 / Chapter 2.1.2 --- Organic Semiconductors Based on N-heteropentacenes: Previous Experimental Results --- p.26 / Chapter 2.2 --- Studied Molecular System: Silylethynylated N-Heteropentacenes --- p.29 / Chapter 2.3 --- Calculation Tool: Selection of Basis Set --- p.33 / Chapter 2.4 --- Results and Discussion --- p.35 / Chapter 2.4.1 --- HOMO and LUMO --- p.35 / Chapter 2.4.2 --- Electron Affinity, Ionization Potential and Reorganization Energy --- p.39 / Chapter 2.4.3 --- The Effect of Dihydropyrazine --- p.42 / Chapter 2.4.4 --- Electron and Hole Mobilities --- p.43 / Chapter 2.5 --- Conclusion --- p.51 / Reference --- p.53 / Chapter Chapter 3 --- Synthesis and Clathrates of Substituted Naphthyltetracenes --- p.57 / Chapter 3.3 --- Introduction --- p.57 / Chapter 3.4 --- Results and Discussion --- p.62 / Chapter 3.5 --- Experimental --- p.67 / Reference --- p.73 / Appendix --- p.74
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_328531 |
| Date | January 2012 |
| Contributors | Mao, Renxin., Chinese University of Hong Kong Graduate School. Division of Chemistry. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, bibliography |
| Format | electronic resource, electronic resource, remote, 1 online resource (vii, 97 leaves) : ill. (some col.) |
| Rights | Use of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
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