蒽桥联的胺-胺电子耦合研究  

Amine-Amine Electronic Coupling through an Anthracene Bridge

作　　者：冯骏[1,2] 邵将洋[1] 龚忠亮[1] 钟羽武[1,2] 

机构地区：[1]中国科学院化学研究所,北京100190 [2]中国科学院大学,北京100149

出　　处：《有机化学》2016年第10期2407-2412,共6页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21271176;21472196;21521062;21501183);中国科学院战略性先导科技专项(No.XDB12010400)资助项目~~

摘　　要：合成了1,5-二(对甲氧基二苯胺)蒽(1)、2,6-二(对甲氧基二苯胺)蒽(2)和9,10-二(对甲氧基二苯胺)蒽(3)三种化合物,对它们的电化学、吸收和发射光谱、光谱电化学以及胺-胺电子耦合开展研究.三种化合物在+0.6^+1.0 V vs Ag/AgCl区域存在两步可逆氧化还原过程,两个氧化还原过程电位差DE在100 mV左右.单电子氧化产物1^(·+)在近红外区域观测到弱价间电荷转移吸收(IVCT),电子耦合常数Vab估算为600 cm^(-1).化合物3^(·+)观测到强IVCT吸收,其Vab估算为1440cm^(-1).单电子氧化产物2^(·+)则没有观测到明显IVCT吸收,表明有机胺在蒽桥基上的取代位置对胺-胺电子耦合程度有重要的影响.Three diamine compounds with an anthracene bridge were synthesized and characterized, including 1,5-bis（di-p-anisylamine）anthracene （1）, 2,6-bis（di-p-anisylamine）anthracene （2） and 9,10-bis（di-p-anisylamine）anthracene （3）. The elec-trochemistry, absorption and emission spectra, spectroelectrochemistry, and amine-amine electronic coupling of these compounds were examined. All compounds display two consecutive redox couples in the potential region between ＋0.6 and ＋1.0 V vs Ag/AgCl, with a potential splitting △E of around 100 mV. In the one-electron-oxidized state, weak intervalence charge transfer （IVCT） transitions were observed for 1^·＋ in the near-infrared （NIR） region and the electronic coupling parameter Vab was calculated to be 600 cm^-1. In contrast, compound 3^·＋ displays an intense IVCT band in the NIR region with a Vab value of 1440 cm^-1. However, no distinct IVCT band was discernable for 2^·＋, indicative of an eligible electronic coupling. This work demonstrates that the positions of the amine substituents on the anthracene bridge play a critical role in determining the degree of amine-amine electronic coupling.

关 键 词：胺 电荷转移 电化学 光化学 

分 类 号：O621[理学—有机化学]