本文選題：有機(jī)半導(dǎo)體 + 六氮雜并五苯�。� 參考：《蘭州大學(xué)》2017年碩士論文

【摘要】：有機(jī)半導(dǎo)體材料相對于無機(jī)半導(dǎo)體材料而言,具有可化學(xué)調(diào)控、易制備等優(yōu)點(diǎn)。有機(jī)半導(dǎo)體材料在輕便、柔性的有機(jī)光電器件中顯示出光明的應(yīng)用前景,引起了人們的廣泛研究,并取得了突破性的發(fā)展。主要表現(xiàn)在具有優(yōu)異性能的有機(jī)半導(dǎo)體分子骨架不斷豐富、器件制備工藝不斷完善等方面。但是目前仍然存在一些挑戰(zhàn),如具有良好空氣穩(wěn)定性、高性能的有機(jī)半導(dǎo)體材料還不是很多,而且對材料結(jié)構(gòu)-性質(zhì)的關(guān)系的研究還不夠深入。因此,設(shè)計(jì)合成新型的有機(jī)共軛骨架對理解結(jié)構(gòu)-性質(zhì)關(guān)系有著重要的意義。在本論文中,我們主要致力于新型、穩(wěn)定的稠環(huán)并苯有機(jī)半導(dǎo)體材料的設(shè)計(jì)與合成。設(shè)計(jì)合成了一種新型的、穩(wěn)定的六氮雜并五苯骨架,深入研究了該化合物的物理化學(xué)性質(zhì);同時(shí),設(shè)計(jì)合成了具有二維結(jié)構(gòu)的芘和傒二酰亞胺衍生物。具體包括以下幾個(gè)部分:1.合成了新型的氫化六氮雜并五苯(Dihydro-1,5,8,12,14-hexaazapentacene,DHHAP)化合物,并研究了其互變異構(gòu)、加酸變色效應(yīng)和芳香性。采用無溶劑的固-固加熱反應(yīng),制備了含有吡啶和吡嗪環(huán)的DHHAP化合物。紫外吸收光譜和核磁共振氫譜研究表明DHHAP在極性溶液中存在benzenoid和quinonoid兩種異構(gòu)體,在酸性介質(zhì)中會(huì)發(fā)生benzenoid構(gòu)型向quinonoid構(gòu)型的轉(zhuǎn)變,并存在兩種質(zhì)子化的醌式結(jié)構(gòu)[DHHAP-q]H22+。DHHAP分子具有很好的穩(wěn)定性,密度泛函理論計(jì)算,包括氫化能、核獨(dú)立化學(xué)位移和各向同性磁感應(yīng)電流密度,表明具有4nπ電子體系的DHHAP化合物具有“全局域芳香性”,因此具有良好的穩(wěn)定性。為了提高DHHAP化合物的溶解性,設(shè)計(jì)了6,13-雙(三異丙基硅基乙炔基)-1,5,7,8,12,14-六氮雜并五苯(TIPS-HAP)骨架,對兩條合成路線進(jìn)行了探索。2.設(shè)計(jì)了具有二維結(jié)構(gòu)的芘和傒二酰亞胺類化合物。采用簡潔的Suzuki偶聯(lián)、分子內(nèi)合環(huán)方法,制備了2,9-二叔丁基二苯并[fg,op]并四苯化合物。對Suzuki偶聯(lián)反應(yīng)條件進(jìn)行了優(yōu)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6,11-二聯(lián)苯-N,N-二十一烷-傒二酰亞胺中間體。2,9-二叔丁基二苯并[fg,op]并四苯在固態(tài)時(shí)仍有很強(qiáng)的熒光,有望用于有機(jī)光敏晶體管中。
[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，

本文編號：1810578