多金属开放位点笼状吡唑配合物的结构与性质研究

本项目拟以具有多金属开放位点的平面型吡唑三核Cu(I)、Ag(I)、Au(I)单元为三角形基本要素, 设计合成多金属开放位点笼状配合物（分子多面体）。通过设计和选择吡唑单元间的连接体，吡唑环上取代基的电子效应和空间位阻效应，运用超分子自组装方法和分子工程学原理，与Cu(I)、Ag(I)、Au(I)金属离子组装合成具有不同几何形状、大小和性质的分子多面体。利用吡唑三核平面单元的多金属开放位点（π酸性）和分子笼的限域空间，针对不同结构特点的分子笼配合物，开展不饱和分子的吸附分离纯化研究，以及催化转化和光功能性质等方面的研究，研究多金属开放位点与限域空间的协同作用对其功能性质的影响。本项目的实施将为研究这类超分子笼状配合物的主客体行为、笼内单分子行为提供实验依据，为探索开发新型功能材料奠定基础，对于研究物质构效关系具有重要意义。

This project focuses on designing and synthesizing a series of cage-like coordination complexes (molecular polyhedra) with multi-metal open sites by using planar trinuclear cyclic Cu(I), Ag(I) or Au(I) pyrazolate coordination units as essential buidling blocks. A series of multi-pyrazole ligands regulated by the geometry and chemical properties of the linkers between the pyrazole units are designed and will be synthesized. Various molecular polyhedra featuring multi-metal open sites with different geometry and size will be prepared by the assembly of such ligands with Cu(I), Ag(I) or Au(I) according to the molecular engineering principle. The structures and properties of these molecular polyhedra will be regulated by the nature of the linkers between the pyrazole units, the electronic effect and steric effect of the substituents on pyrazole rings, and the metal. Further, by taking advantages of the multi-metal open sites of the trinuclear Cu(I), Ag(I)or Au(I) pyrazolates units and the confined space inside these coordination cage-like complexes, this project will explore the influence of synergistic effect of the multi-metal open sites with confined space on their properties such as adsorption, separation, purification of unsaturated molecules, catalysis, and photofunctional properties. The implementation of this project is expected to provide experimental evidences for the host-guest and single molecular behaviors inside the cages, and to set a foundation for exploring novel functional materials and devices. Also it will be of great significance for the investigation on the structure-property relationship of transition metal coordination compounds.