摘要
以4-{2-[4-N,N-二（4-甲基苯基）氨基苯基]乙烯基}苯甲醛为原料,首先经过缩合反应,得到系列带有含氮基团的还原底物,再利用金属硼氢化试剂对极性双键的选择性还原特征,合成了系列饱和柔性烷基链修饰的三苯胺氨基衍生物（Ⅱb^d）。通过控制反应时间和加料顺序、梯度增强还原剂还原能力等方式对合成路线进行了优化。实验结果表明,硼氢化钠在-5℃下能够对硝基相邻双键进行高效还原,而氰基相邻双键极性较小需要采用硼氢化锂在80℃下回流10h进行还原。最后将得到的氨基衍生物与均三嗪基团相连,得到系列给体-受体（D-A）化合物（Ⅲb^d）,利用核磁氢谱、碳谱、高分辨质谱以及红外吸收光谱对其进行了结构表征。通过分析紫外-可见吸收,荧光发射光谱,并结合相关电化学数据可知,此系列化合物可产生光诱导长寿命电荷分离态,在有机光电领域具有一定的应用前景。
A series of saturated alkyl chain decorated triphenylamine amino derivatives（Ⅱb^d） were constructed through condensation reaction and selective reduction of polar double bond with metal boron hydride reactants using 4-{2-[N, N-bis（4-methylphenyl） aminophenyl]ethenyl}-benzaldehyde as starting materials. The synthetic route was optimized by controlling reaction time and charging sequence, gradient strengthening reductive ability of reductant and so on. The results showed that the ortho double bond of nitro group can be efficiently reducted with sodium borohydride at –5 ℃. However reduction of the ortho double bond of cyano group requires lithium boronhydride at 80 ℃ for as long as 10 h. Finally, the triphenylamine amino derivates were linked to electron-deficient nitrogen heterocyclic unit（1,3,5-triazine） to form the corresponding covalently linked donor-acceptor（D-A） dyads（Ⅲb^d）. These products were characterized by ~1 HNMR, ^（13） CNMR, high resolution mass spectrometry and infrared absorption spectroscopy. The results of UV-vis absorption, fluorescence emission and electrochemical measurements reveal that these dyads can form long-lived charge-separated state and have certain application prospect in organic photovoltaic devices.
作者
李平安
周雪琴
谢佳轩
刘东志
李巍
汪天洋
LI Ping-an;ZHOU Xue-qin;XIE Jia-xuan;LIU Dong-zhi;LI Wei;WANG Tian-yang(School of Chemical Engineering and Technology,Tianjin University,Tianjin 300350,China;Tianjin Key Laboratory of 4olecular Optoelectronic Sciences,School of Science,Tianjin University,Tianjin 300072,China;Collaborative Innovation ？enter of Chemical Science and Engineering,Tianjin University,Tianjin 300072,China;Tianjin Engineering Research ？enter of Functional Fine Chemicals,Tianjin 300350,China)
出处
《精细化工》
EI
CAS
CSCD
北大核心
2018年第11期1801-1808,1816,共9页
Fine Chemicals
基金
国家自然科学基金(21506151,21576195,21776207)~~
关键词
烷基柔性链
三苯胺氨基衍生物
分子内电荷转移
D-A化合物
功能材料
flexible alkyl chain
triphenylamine amino derivates
intramolecular charge transfer
D-A dyad
functional materials
