氰基取代苯乙烯基化合物的合成及光物理性能研究

摘要

Cyano group is a strong electron-withdrawing substituent.Introduction of the cyano group can reduce the lowest unoccupied molecular orbital (LUMO) level and the energy bandgap (Eg).Two compounds 1-(4-(4-cyano-6-chloro-1,3,5-triazine) aminophenyl)-2-(4-N,N'-di (p-tolyl) phenylamino)ethylene (MTPA-TRCc1) and 1-(4-(4,6-dicyano-1,3,5-triazine) aminophenyl)-2-(4-N,N'-di (p-tolyl) phenylamino) ethylene (MTPA-TRCc2) were synthesized from the parent molecule 1-(4-(4,6-dichloro-1,3,5-triazine) aminophenyl)-2-(4-N,N'-di (p-tolyl) phenylamino) ethylene (MTPA-TRC).Chlorine atoms of the triazine (TRC) were substituted by cyano groups.The structures of the two compounds were confirmed by 1H NMR,ESI high resolution mass spectrometry and infrared spectroscopy.Detailed experiment was conducted to study the influence of the reaction temperature,time and feed ratio on the yields and the optimum synthetic conditions were achieved.Photophysical and electrochemical properties were studied by UV-vis absorption spectroscopy and cyclic voltammetry.Calculated energy levels of the compounds were obtained through computational methods.The results reveal that one cyano group may reduce the LUMO level and Eg of MTPA-TRCc1 whereas another cyano group in MTPA-TRCc2 only exerts a bit effect.MTPA-TRCc1 shows the strongest absorbance and intramolecular charge transfer (ICT) degree.%氰基具有强吸电子性,氰基的引入能够降低化合物的最低未占分子轨道(LUMO)能级和能隙(Eg).以1-(4-(4,6-二氯-1,3,5-三嗪)氨基苯基)-2-(4-N,N'-二(甲基苯基)苯胺基)乙烯(MTPA-TRC)为母体,对均三嗪(TRC)上的氯进行氰基取代,合成了1-(4-(4-氰基-6-氯-1,3,5-三嗪)氨基苯基)-2-(4-N,N'-二(对甲基苯基)苯胺基)乙烯(MTPA-TRCc1)和1-(4-(4,6-二氰基-1,3,5-三嗪)氨基苯基)-2-(4-N,N'-二(对甲基苯基)苯胺基)乙烯(MTPA-TRCc2),其结构得到1 H NMR、ESI高分辨质谱及红外光谱等表征.研究了反应温度、时间和投料比对反应收率的影响,得到该反应的最适宜反应条件.通过紫外-可见吸收光谱,循环伏安测试分析其光物理及电化学性能,并结合计算化学得到了各化合物的计算能级.研究结果表明,1个氰基的引入可明显降低了化合物的LU-MO能级及能隙Eg,但第2个氰基的进一步作用效果却很小;MTPA-TRCc1表现出最强的吸光度以及分子内电荷转移程度.