分子内电荷转移化合物自组装功能体系  

Self-assembly of functional molecular systems based on intramolecular charge-transfer compounds

作　　者：贾志宇[1,2] 李勇军[1,2] 刘辉彪[1,2] 李玉良[1,2] 

机构地区：[1]中国科学院化学研究所,中国科学院有机固体重点实验室,北京分子科学国家实验室,北京100190 [2]中国科学院大学,北京100049

出　　处：《中国科学：化学》2016年第10期1050-1063,共14页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:21322301);国家重点基础研究发展计划(编号:2012CB932901);中国科学院战略性先导科技专项(编号:XDA09020302,XDB12010300)资助项目

摘　　要：本文综述了基于电荷转移作用的具有特定组装结构的功能分子体系的合成、自组装过程和性质.易于组装且结构-性能关系清晰的分子内电荷转移化合物的分子设计可以用来开发新颖的功能体系.我们阐述了通过在π共轭体系中引入杂环或杂原子或通过使用其他芳香环扩展芳香体系的共轭长度等方法合成分子内电荷转移化合物.分子内电荷转移化合物的给体/受体以及其连接基团极大地影响有机聚集体的形貌、尺寸和其光化学性能.非中心对称的超细纤维结构的独立非线性光学响应能够在光谱上和空间上被分离和调控;分子内电荷转移化合物的另一个应用是发展基于分子内电荷转移过程效率调控的分子传感器.通过分子内电荷转移化合物的可控自组装将获得新的或改进的化学和物理性质,该方法将被广泛应用于光学、电学和光电子领域.Highly polarized compounds exhibiting intramolecular charge transfer（ICT） are used widely as nonlinear optical（NLO） materials and red emitters and in organic light emitting diodes.Low-molecular-weight donor/acceptor（D/A）-substituted ICT compounds are ideal candidates for use as the building blocks of hierarchically structured,multifunctional self-assembled supramolecular systems.This paper describes our recent studies into the development of functional molecular systems with well-defined self-assembled structures based on charge-transfer（CT） interactions.We have developed new methods to synthesize ICT compounds through the introduction of heterocycles or heteroatoms to the π-conjugated systems or through extending the conjugation of diverse aromatic systems via another aromatic ring.For example,we obtained a noncentrosymmetric microfiber structure that possessed a permanent dipole along its fibers＇ long axis and a transition dipole perpendicular to it;the independent NLO responses of this material can be separated and tuned spectroscopically and spatially.The encouraging results that we have obtained suggest that such self-assembled ICT molecular materials can guide the design of new nanostructures and materials from organic systems,and that these materials,across a range of compositions,sizes,shapes,and functionalities,can potentially be applied in the fields of electronics,optics,and optoelectronics.

关 键 词：分子内电荷转移 自组装 共轭体系 合成 光学性质 

分 类 号：O641[理学—物理化学]