基于有机聚合物/多酸的圆偏振发光杂化复合材料

Circularly polarized luminescent materials are a type of important chiral materials. Chiral organic molecules, Lanthanide complexes and can display CPL with dectectable glum values, while the inorganic-organic hybrid materials are still rare and the mechanism is unclear. In this proposal, we propose to develop a facile supramolecualr strategy to prepare CPL materials with high luminescent intensity and high glum value based on chiral polymers and lanthanide-containing polyoxometalates. Lanthanide ions have a magnetic dipole-allowed electric dipole-forbidden transition which is promising to achieve a high glum. We plan to fabricate the assembles of positive organic chiral polycations and anionic polyoxometalates through electrostatic interactions, investigate the relationship between the assembly behavior and their CD in the ground state and CPL properties in the excited states, discover the mechanism of chiral transfer and CPL emssion in the hybrid system with the assistance of the computer simulations based on simplified models. Since the hybrid system based on non-covalent interaction would be responsive to multiple stimuli, such as pH, small ions, solvent, or the electrochemical method, we also propose to investigate the CPL responsiveness to those stimuli and further develop its application in sensors based on sensitive detection of CPL signals.

圆偏振发光（CPL）材料是一类重要的手性材料，手性有机分子、镧系金属配合物、有机无机杂化体系都呈现出CPL性质，但杂化体系存在不对称因子低，发光机制还不明确。本项目申请将发展简单普适的超分子构筑方法来获得高CPL的杂化复合材料。镧系元素发光谱带包含磁允许电禁阻的跃迁，有可能得到高的CPL。我们选取有机聚合物作为手性源，无机含镧系金属多酸为发光基元，以静电相互作用为主要驱动力构筑超分子有序体系。考察其在基态和激发态下的手性性质，探索超分子结构与CPL性质之间的构效关系，制备具有发光效率高、glum数值大的CPL材料；探索具有CPL性质复合体系中的手性传递规律，结合实验与计算机模拟从微观分子水平上揭示手性传递和CPL发光机制；研究在pH、离子、溶剂、电化学等刺激下对CPL性质的调控，进而开发基于CPL的化学检测器。

本项目研究工作着力于发展聚合物/多酸有机无机杂化圆偏振光材料的构筑及性能调控。（1）以含刚性手性侧基的聚合物诱导杂多酸的圆偏振发光：通过静电自组装构筑具有刚性侧基结构的阳离子嵌段共聚物/非手性杂多酸,首次手性诱导发光多酸产生圆偏振光；（2）银纳米粒子掺杂的圆偏振发光杂化材料：利用银纳米粒子的表面等离子工作效应，增强了柔性嵌段聚合物/发光多酸复合体系的圆偏振荧光；（3）天然高分子/多酸的圆偏振荧光材料：以具有光子晶体性质纤维素纳米晶为模板，利用其选择反射性质诱导出多酸产生具有高不对称因子的圆偏振荧光。（4）光响应性的圆偏振荧光体系：利用主客体作用和静电作用，构筑了基于偶氮苯/环糊精/多酸的光响应组装体，实现了复合体系基态和激发态诱导手性的具有可逆光响应性。