基于苯并噻二唑的二维多环芳烃共轭分子的设计合成及应用

发布时间：2018-01-05 16:03

本文关键词：基于苯并噻二唑的二维多环芳烃共轭分子的设计合成及应用　出处：《南京邮电大学》2016年硕士论文　论文类型：学位论文

【摘要】：近年来,随着对多环芳烃研究的不断深入,有机光电材料发展迅速。众所周知对于多环芳烃材料,π共轭体系的增加可以提高分子的器件性能。而随着π共轭程度不断增加,稳定性越来越差,目前的解决方式是通过在并苯体系中引入高电负性原子或强吸电子基团,降低HOMO能级,提高分子稳定性,从而提高其器件性能。在此基础上,为了获得性能优越的多环芳烃材料,我们以5,6-二溴苯并噻二唑为核心单元展开了工作,并取得了以下研究成果:(1)在确定了5,6-二溴苯并噻二唑为核心之后,因为5,6-二溴苯并噻二唑两个溴相邻,所以我们选择通过炔键环化的方式来拓展二维共轭体系。为了保证材料的溶解性,和更有效的电荷传输,我们选择了烷基噻吩和双烷氧基苯为取代基,通过C-H活化,Suzuki偶联,Sonogashira偶联等方法构建了两个炔偶联中间体4a,4b。在二氯化铂的作用下我们得到了炔键与一侧取代基构成六元环的产物5a,5b。我们通过Scholl反应进一步使其变成了产物6a,6b,当然其中有一些副反应的产生。而4a,4b在二氯化钯催化作用下与两边取代基都构成了五元环的结构即8a,8b,但有异构体的存在。最后通过芴酮偶联的方法证实了炔键与两边取代基生成了双边五元环。这项工作使我们对炔键环化的特性有了深入了解,为以后使用该方法拓展π体系奠定基础。(2)以Stille偶联反应和Scholl反应为主要手段合成了16a和16b两个螺烯类高度扭曲的共轭分子,二面角达到了44.8°。16a与16b主体结构一样,唯一区别在于烷基链的不同,16b选用C10支链,溶解性优于16a,而两个材料经溶液(氯仿)旋涂方法制备了场效应晶体管器件却差别很大,16b测得的空穴迁移率为3.27×10-2 cm2 V-1 s-1,16a测得的空穴迁移率为1.95×10-4 cm2 V-1 s-1。证明烷基链不光能影响溶解性,还能改变堆积方式。(3)设计并合成了一系列基于苯并噻二唑的线性晶体管材料,结构简单,合成简便,但却具有很好的晶体管性能,其中测得FTC8(7b)的空穴迁移率达到0.177 cm2 V-1 s-1,开关比为8.32×105。而化合物TFTC12(7a)的空穴迁移率测到0.070 cm2 V-1 s-1,开关比为2.92×104。这样的简单结构获得这样的性能,性价比非常高。而且由于TFTC12(7a),FTC8(7b)是以芴酮的形式存在,HOMO分别为-6.13 e V和-5.85 e V,稳定性非常好。
[Abstract]:In recent years, with the development of polycyclic aromatic hydrocarbons (PAHs), organic optoelectronic materials have developed rapidly. The increase of 蟺 conjugated system can improve the performance of molecular devices, but with the increasing of 蟺 conjugation degree, the stability becomes worse and worse. The current solution is to reduce the HOMO energy level and improve the molecular stability by introducing high electronegativity atoms or strong electron-absorbing groups in benzene system. In order to obtain high performance polycyclic aromatic hydrocarbons (PAHs) materials, we have carried out the work with 5C6-dibromobenzo-thiadiazole as the core unit, and obtained the following research results: 1) in the determination of 5. After 6-dibromobenzo-thiadiazole is the core, because 5-bromo-6-dibromobenzo-thiadiazole is adjacent to two bromins, we choose to expand the two-dimensional conjugate system by cyclization of acetylene bond, in order to ensure the solubility of the material. And more efficient charge transport, we selected alkyl thiophene and dialkoxy benzene as substituents, and activated Suzuki coupling by C-H. Two alkyne coupling intermediates 4a- 4b have been constructed by Sonogashira coupling method. Under the action of platinum dichloride, we have obtained the product of acetylene bond and one substituent group to form a six-member ring for 5a. 5b.We further made the product 6aah6b by Scholl reaction, and of course there were some side reactions. And 4a. The structure of the quaternary ring is 8a ~ (8) b, which is composed of 4b and the substituents of both sides under the catalysis of palladium dichloride (PD _ (2)). But there are some isomers. Finally, it is proved by the method of fluorenone coupling that the acetylene bond and the two side substituents form a two-sided quaternary ring. This work has made us understand the characteristics of the ring of acetylene bond in depth. It will lay a foundation for the extension of 蟺 system by this method in the future. Two highly twisted conjugated spiroenes, 16a and 16b, were synthesized by Stille coupling reaction and Scholl reaction. The dihedral angle of 44.8 掳. 16a is the same as the main structure of 16b. The only difference is that the C10 branched chain is chosen for different alkyl chain and the solubility is better than that of 16a. However, the hole mobility measured by 16b is 3.27 脳 10 ~ (-2) cm2 V-1 s ~ (-1). The hole mobility measured in 16a is 1.95 脳 10 ~ (-4) cm2 V-1 ~ (-1) s-1.It is proved that alkyl chain can not only affect solubility. A series of linear transistors based on benzothiadiazole have been designed and synthesized, which are simple in structure and simple in synthesis, but have good transistor performance. The hole mobility of FTC8 (7b) was 0.177 cm2 V-1 s-1. The switching ratio is 8.32 脳 10 ~ 5. The hole mobility of compound TFTC _ (1210 ~ (7)) is 0.070 cm2 V ~ (-1) s ~ (-1). The switching ratio is 2.92 脳 10 ~ (4). The performance of this simple structure is very high. Moreover, the TFTC _ (12) / 7a ~ (-1) FTC _ (8) B) exists in the form of fluorenone. The HOMO is -6.13 EV and -5.85 EV, respectively, and the stability is very good.
【学位授予单位】：南京邮电大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TN304;O621

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