柔性链修饰三苯胺氨基衍生物的构建策略研究

Construction strategy of flexible chain decorated triphenylamine amino derivatives

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则需要采用硼氢化锂在80℃下回流10 h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。

Abstract:

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. The results show 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. The products were characterized by 1HNMR, 13CNMR, high resolution mass spectrometry and infrared absorption spectroscopy. The results of UV-vis absorption, fluorescence emission and electrochemical measurements reveal the potential of these dyads to form long-lived charge-separated state for the application in photovoltaic devices.