共轭高分子圆偏振荧光的智能调控—从单分子手性到宏观螺旋

The development of the novel organic circularly polarized light-emitting materials for the construction of intelligent and multifunctional optoelectronic devices has become a hotspot research for optoelectronics. In the current circularly polarized luminescence systems, the key issue is how to use rigid conjugated polymers as functional building blocks to construct well-regulated hierarchical aggregates in order to intelligently control circularly polarized luminescence, and those challenges have seriously restricted their further research and applications as organic photo-electronic materials. With the aim of solving the above problems, construction of well-regulated hierarchical aggregates could tune circularly polarized luminescence employing the strategy of controlling self-assembly. To tune circularly polarized luminescence of polymer intelligently, two strategies could be applied to produce the materials with different-levels of hierarchy. The self-assembly of the conjugated polymers into hierarchical aggregates can be assisted by the Pt•••Pt, electrostatic, metal coordination and π•••π interactions among the π-conjugated polymer, the chiral compound and the π-conjugated polymer. The effects of the modification of chiral micro-environment for constructing ordered aggregates will be theoretically explored by combining the results of quantum chemical calculations and experimental data. In addition, the mechanism of transfer and amplification of chiral information into an ordered aggregates and the driving force for tuning circularly polarized luminescence will be further investigated. The above research in this field will provide both the theoretical and experimental methods and basis for the development of smart and multifunctional organic optoelectronic devices.

新型有机圆偏振材料的开发及其智能化、多功能化是光电材料等领域研究热点。目前，制约有机圆偏振光进一步发展及应用的关键科学问题是如何利用刚性共轭高分子构筑多层次有序聚集体，实现圆偏振荧光的智能调控。本项目针对上述遇到的问题，提出通过自组装技术构建高分子多层次有序聚集体调控圆偏振荧光概念。通过对手性高分子结构改性和运用手性分子诱导高分子的策略，利用Pt•••Pt弱相互作用、金属配位作用、静电相互作用与分子间的π•••π弱相互作用的协同效应，制备高分子多层次有序聚集体，实现对圆偏振荧光智能调控。结合量子化学理论计算和实验数据，探索高分子微观结构环境的修饰对构筑多层次有序聚集体的影响，探讨手性在整个有序聚集体中的传递、非线性放大机制，深入探究圆偏振光机制智能调控的机制，为进一步发展圆偏振光电材料的智能化和多功能化提供实验和理论上的方法和依据。

本研究课题设计和制备了几种π-共轭有机光电材料，主要研究手性微观结构的变化对手性传递、非线性放大机制及有序聚集体堆积结构方式的影响，探索圆偏振荧光变化的内在因素。引入结构导向性强的手性官能团，能够改变分子的微观结构和分子间的堆积方式。通过实验和量子化学计算研究，实现了单分子态的圆偏振荧光，且光学活性聚集体的形成与圆偏振荧光信息的变化密切相关，达到了智能调控有机偏振荧光的目的，更重要的是，直接旋涂未经煺火处理的有机薄膜获得了比较强的圆偏振荧光信号，为进一步发展圆偏振光电材料的智能化和多功能化提供了实践和理论的依据与支撑。