圆偏振光对手性配位聚合物立体构型的调控机制

In recent years, chiral coordination polymers have attracted much attention due to their potential applications in molecular recognition/sensing/separation, asymmetric catalysis, non-linear optical and electronic materials. The design and construction of functional chiral coordination polymers, as well as the configuration modulation, are of great importance for practical view. In this context, develop a modulation strategy that based on structural chemistry principle and optical feature of chiral compounds, find out the key factors to modulate the configuration is an essential scientific issue. In this project, based on the principle of coordination self-assembly and the optical property for chiral agents, the circularly polarized light is adopted as chiral source during the self-assembly process to study the enantioselective modulation of chiral coordination polymers by the help of chiral amplification effect of ordered self-assembly. By studying and comparing the systems that with or without the chiral agents, the chiral coordination self-assembly will be learned, as well as the mechanism of enantioselective modulation of circularly polarized light during the reaction and crystallization procedure. It is hopeful to provide a new perspective for the theories of chiral induction and chiral amplification from the view of structural chemistry and coordination chemistry, a new family of functional chiral coordination polymers, as well as a new strategy for their steric configuration modulation.

手性配位聚合物因在分子识别/传感/分离、不对称催化、非线性光电材料等领域有潜在的应用价值一直是近年来国内外研究热点之一。基于功能需求的手性配位聚合物的设计构筑以及构型调控对于其实现广泛应用具有重要意义。因此发展一个基于结构化学原理及手性物质光学活性的调控方法，找到影响立体构型的关键因素是重要科学问题。本项目立足于配位自组装原理，提出利用手性物质对左右圆偏振光吸收系数的差异，以圆偏振光作为组装过程的手性源，通过有序自组装的手性放大作用达到对手性配位聚合物立体构型有效调控的新思路。研究对比基于手性分子的体系与非（潜）手性分子的体系之间的差别，探寻手性配位自组装途径，揭示圆偏振光辐照对反应结晶过程中构型选择的作用机制。通过本项目的研究，望能从结构化学、配位化学的角度为手性立体化学中手性诱导、手性放大等理论提供新的视角，为开发功能导向的手性配位聚合物提供研究素材，并为其立体构型调控提供一种新策略。

近年来，人们关于手性配位聚合体系的研究已从早期的晶态聚合物材料扩展到非晶态的甚或纳米尺度的配位超分子的研究，并在手性识别与分离、手性光学性质（例如圆二色性、圆偏振荧光等）方面发现了重要的应用前景。然而，实验室合成手性配位聚合晶态材料或软材料往往都有一个重要的挑战，即如何克服产物外消旋的趋势。因此，相关研究往往依赖于采用单一构型的手性试剂。这显然会限制研究的边界与深度。本课题选择的是应用圆偏振光或涡流等物理作用作为手性外场，研究了这类手性外场对非手性底物出发的化学反应如何产生影响，观察到一例手性配位聚合物的圆偏振光照响应，三例非手性配位聚集体系在涡流场中的动态手性排布及其基态与激发态光谱性质，并探讨了基于潜手性配体的配位自组装及其性质。通过本项目的研究，望能为物理外场调控手性配位聚集体系提供一些研究素材，从中启发一些关于手性物理场与手性物质相互作用的研究。