手性有机金属簇的合成与组装

Chiral metal clusters, featured by the aggregation of several interactive metal atoms and their asymmetric arrangements, are conducive to expanding the scope of functional chiral molecules, developing chiral cluster-based catalysts and fabricating chiroptical functional materials. In this project, we propose to in situ construct organic polyanionic species by virtue of organic asymmetric synthetic methods, which will be further applied to synthesize chiral metal clusters by electrostatic attraction and coordination. Furthermore, chiral anions and ligands are also employed to construct chiral metal clusters based on a chirality-transfer strategy. With these structurally well-defined and finely tunable chiral metal clusters in hand, we try to correlate their structural details with circular dichroism response and circular polarized luminescence. In addition, supramolecular assembly of chiral metal clusters and the related chirality transfer and amplification process from molecules to supramolecular assembled entities will be explored as well. In summary, through the study of this project, we hope to develop a new and efficient synthetic method for chiral metal clusters, clarify the mechanism concerning the chirality transfer and amplification within chiral metal clusters and ultimately establish a new and fundamental research system for chiral metal clusters with our own characteristics.

含有多个相互作用且呈不对称排列金属离子的手性金属簇化合物，对于拓展新的手性分子结构形式、发展手性金属簇催化剂、开发手性光学材料具有重要意义。本申请项目拟借鉴有机不对称合成方法，利用有机反应原位构筑负电荷位点分散的手性有机多负离子，进而合成手性多核金属簇化合物。同时，本项目也将发展利用手性阴离子或手性配体进行手性传递构筑手性金属簇的新方法。基于这些结构明确且可调节的手性金属簇化合物，我们拟建立这类化合物的结构与其圆二色吸收及圆偏振发光性质之间的关系。此外，我们也将深入探索手性金属簇的多级组装过程，探索金属簇分子手性如何传递、放大至超分子手性并且影响组装体性质。通过本项目的研究，我们希望建立手性金属簇化合物的精准构筑方法，厘清分子单体与组装体手性之间的传递、放大机制，建立具有自身特色的手性金属簇研究体系。

手性金属簇的合成与组装研究不仅可以拓展手性化合物的结构类型，推动人们对物质手性的认识和理解，同时也将拓展其在手性光学材料、手性催化等领域的应用。在本重大研究计划培育项目支持下，我们建立了基于有机原位反应的手性金属簇精准构筑方法，以有机原位反应所产生的多负离子为模板，调控金属离子空间排布构筑了S型、螺环型等多种手性有机金属簇新结构；利用外加手性阴离子与金属簇单元作用，实现了由外向内的手性传递，初步阐明了手性诱导试剂或基团向金属簇进行手性传递的机制与规律；通过比较不同核数与构型的手性金属簇结构与性质，建立了金属-金属作用以及多金属排布扭转角与其圆二色性质之间的关系，阐明了金属离子手性排列增强其圆偏振发光性能的机制。本项目结合了金属有机化学和超分子化学研究方法，考察了手性金属簇的合成、结构及其性质，推动了手性有机金属簇这一特色研究方向的建立和发展。