氢化六氮杂并五苯和芘类有机半导体材料的设计与合成

发布时间：2018-04-27 11:36

  本文选题：有机半导体 + 六氮杂并五苯　； 参考：《兰州大学》2017年硕士论文

【摘要】：有机半导体材料相对于无机半导体材料而言,具有可化学调控、易制备等优点。有机半导体材料在轻便、柔性的有机光电器件中显示出光明的应用前景,引起了人们的广泛研究,并取得了突破性的发展。主要表现在具有优异性能的有机半导体分子骨架不断丰富、器件制备工艺不断完善等方面。但是目前仍然存在一些挑战,如具有良好空气稳定性、高性能的有机半导体材料还不是很多,而且对材料结构-性质的关系的研究还不够深入。因此,设计合成新型的有机共轭骨架对理解结构-性质关系有着重要的意义。在本论文中,我们主要致力于新型、稳定的稠环并苯有机半导体材料的设计与合成。设计合成了一种新型的、稳定的六氮杂并五苯骨架,深入研究了该化合物的物理化学性质;同时,设计合成了具有二维结构的芘和傒二酰亚胺衍生物。具体包括以下几个部分:1.合成了新型的氢化六氮杂并五苯(Dihydro-1,5,8,12,14-hexaazapentacene,DHHAP)化合物,并研究了其互变异构、加酸变色效应和芳香性。采用无溶剂的固-固加热反应,制备了含有吡啶和吡嗪环的DHHAP化合物。紫外吸收光谱和核磁共振氢谱研究表明DHHAP在极性溶液中存在benzenoid和quinonoid两种异构体,在酸性介质中会发生benzenoid构型向quinonoid构型的转变,并存在两种质子化的醌式结构[DHHAP-q]H22+。DHHAP分子具有很好的稳定性,密度泛函理论计算,包括氢化能、核独立化学位移和各向同性磁感应电流密度,表明具有4nπ电子体系的DHHAP化合物具有“全局域芳香性”,因此具有良好的稳定性。为了提高DHHAP化合物的溶解性,设计了6,13-双(三异丙基硅基乙炔基)-1,5,7,8,12,14-六氮杂并五苯(TIPS-HAP)骨架,对两条合成路线进行了探索。2.设计了具有二维结构的芘和傒二酰亚胺类化合物。采用简洁的Suzuki偶联、分子内合环方法,制备了2,9-二叔丁基二苯并[fg,op]并四苯化合物。对Suzuki偶联反应条件进行了优化探索,并成功合成了2,9-二叔丁基二苯并[fg,op]并四苯化合物和6,11-二联苯-N,N-二十一烷-傒二酰亚胺中间体。2,9-二叔丁基二苯并[fg,op]并四苯在固态时仍有很强的荧光,有望用于有机光敏晶体管中。
[Abstract]:Compared with inorganic semiconductor materials, organic semiconductors have the advantages of chemical control and easy preparation. Organic semiconductor materials have shown a bright application prospect in light and flexible organic optoelectronic devices, which has caused extensive research and made a breakthrough development. It is mainly reflected in the abundance of organic semiconductor molecular skeleton and the perfection of device fabrication technology. However, there are still some challenges, such as good air stability, high performance organic semiconductor materials are not many, and the relationship between structure and properties of materials is not sufficiently studied. Therefore, the design and synthesis of a novel organic conjugate skeleton is of great significance in understanding the structure-property relationship. In this thesis, we focus on the design and synthesis of novel, stable dense ring benzenes organic semiconductors. A novel stable hexaazobenzene skeleton was designed and synthesized, and the physical and chemical properties of the compound were studied. At the same time, pyrene and diimide derivatives with two-dimensional structure were designed and synthesized. It includes the following parts: 1. A new hydrohexaazapentacenetriol (DHHHAPP) compound was synthesized, and its tautomerism, acid chromism and aromaticity were studied. DHHAP compounds containing pyridine and pyrazine ring were prepared by solvent-free solid-solid heating reaction. UV absorption spectra and nuclear magnetic resonance (NMR) hydrogen spectra showed that there were two isomers of benzenoid and quinonoid in polar solution of DHHAP, and the transition of benzenoid configuration to quinonoid configuration occurred in acid medium. There are two kinds of protonated quinone structure [DHHAP-q] H22. DHHAP molecules have good stability, density functional theory calculation, including hydrogenation energy, nuclear independent chemical shift and isotropic magnetic induction current density, It is shown that the DHHAP compounds with 4n 蟺 electron system have "global domain aromaticity", so they have good stability. In order to improve the solubility of DHHAP compounds, two synthetic routes were explored. Pyrene and diimide compounds with two-dimensional structure were designed. Suzuki coupling and intramolecular ring method were used to prepare dibenzo (FG) O (2) -dibenzo (FG) (2) -tert- (2) -tert- (鈪，

本文编号：1810578