过渡金属功能化的多重发光分子开关

A new family of metal organic complex with on-off switch effect can be developed by using suitable metal ions and organic ligands, and their application in the area of metal organic photoelectric materials will be further investigated. Incorporating the metal moiety into the dithienylethene switches can limit the intramolecular energy transfer between the molecular switches, and a new multistep and/or multiple on-off photoswitch system can be achieved. Another strategy is to introduce the functional lanthanide unit into the metal-coordinated photoswitch systems. The degree of energy transfer from the transition metal chromophore to lanthanide moiety can be regulated by controlling the on-off states of the dithienylethene unit, which will lead to double light emission with two complementary colors, and achieve novel white light emitting materials with super-high luminous efficacy.

通过金属离子的选择及合理的有机配体设计，合成新颖的具有on-off开关效应的金属有机配合物，系统开展其在光电信息材料领域的研究。将金属砌块引入到含多个二芳基乙烯分子开关单元的有机体系内，抑制相邻分子开关单元间的能量传递，实现具有分步及多重开关效应的光化学反应体系。在具有分子开关效应的过渡金属配合物中引入稀土金属砌块，通过桥联配体开关效应调控过渡金属发色团到稀土中心能量的传递程度，实现分子双重发射互补光，获得新型高效白光发射材料。

本项目开展具有多重光致变色行为的过渡金属配合物的设计合成及光电性能调控等方面的工作。利用具有氧化还原活性的[Cl(dppe)2Ru]+砌块与两个相同或不同的二芳基乙烯结构单元连接制备对称及不对称钌二芳基乙烯金属配合物，金属砌块作为隔离基抑制二芳基乙烯元件间的能量传递而实现分步及选择性光致变色，改变金属价态能够使二芳基乙烯分子关环吸收峰发生显著移动,且二芳基乙烯配体关环吸收越红移越有利于发生分步光致变色并获得双（多）重关环产物；利用金属离子作为桥头单元连接二硫二噻吩合成一系列含单个或两个DTE结构单元的金属开关配合物。相对于光化学惰性的镍双二硫二噻吩开关，锌双二硫二噻吩具有明显的分步光致变色现象。只有当二硫二噻吩作为双阴离子才可实现其金属配合物的可逆光致变色，而单阴离子或中性的二硫二噻吩金属配合物无法观察到光致变色现象。