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第 35 卷第 11 期 精 细 化 工 Vol.35, No.11
2018 年 11 月 FINE CHEMICALS Nov. 2018

功能材料
柔性链修饰三苯胺氨基衍生物的构建策略

李平安 1,3 ，周雪琴 1,3,4 ，谢佳轩 1,3 ，刘东志 1,3,4 ，李 巍 1,3,4 ，汪天洋 1,2,3*

（1. 天津大学 化工学院，天津 300350；2. 天津市分子光电科学重点实验室，天津大学 理学院，天津 300072；
3. 天津化学化工协同创新中心，天津 300072；4. 天津市功能精细化学品技术工程中心，天津 300350）

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 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。
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
中图分类号：O621.2 文献标识码：A 文章编号：1003-5214 (2018) 11-1801-09

Construction Strategy of Flexible Chain Decorated
Triphenylamine Amino Derivatives

1,3
1,3
LI Ping-an , ZHOU Xue-qin 1,3,4 , XIE Jia-xuan , LIU Dong-zhi 1,3,4 ,
LI Wei 1,3,4 , WANG Tian-yang 1,2,3*
（1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China; 2. Tianjin Key Laboratory of
Molecular Optoelectronic Sciences, School of Science, Tianjin University, Tianjin 300072, China; 3. Collaborative Innovation
Center of Chemical Science and Engineering, Tianjin University, Tianjin 300072, China; 4. Tianjin Engineering Research
Center of Functional Fine Chemicals, Tianjin 300350, China）

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 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
1
characterized by 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.
Key words: flexible alkyl chain; triphenylamine amino derivates; intramolecular charge transfer; D-A dyad;
functional materials

收稿日期：2017-11-06; 定用日期：2018-03-28; DOI: 10.13550/j.jxhg.20170906
基金项目：国家自然科学基金（21506151, 21576195, 21776207）
作者简介：李平安（1992—），男，硕士生。联系人：汪天洋（1988—），副教授，E-mail：tianyangwang@tju.edu.cn。