多金属开放位点笼状吡唑配合物的结构与性质研究

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.

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。

本项目主要围绕多金属开放位点的功能配合物为目标，通过设计双配位功能吡唑和双吡唑两类吡唑配体，用溶剂热直接合成和溶剂热后合成转化的方法，制备合成了一系列以三核吡唑铜Cu3Pz3为基本结构单元的三金属开放位点的光功能配合物。利用配体上的第二配位点（吡啶、四氮唑），制备出了一系列以碘铜簇和Cu3Pz3为基本结构单元的双原子簇配合物，研究了配体上的取代基的电子效应和空间效应对碘铜簇大小的调控作用和对配合物聚集形态的影响；通过晶体转化策略研究了辅助配体分子的结构对配合物结构和发光性质的影响；通过辅助配位的抗衡阴离子对配合物的二元发光性质进行了调控，实现了化学调色板效应。利用Cu3Pz3弱的π酸性的特点，用芳香簇小分子、以及Cu2I2平面配位单元作为模板剂，诱导了多种形式的三棱柱笼状超分子配合物，研究了客体分子的结构及其电子效应对配合物结构和发光性质的影响，并且通过后合成配体取代反应对三棱柱状配合物的几何形状和嵌套结构进行了调控。本项目已经发表SCI研究论文5篇，包括2篇Inorganic Chemistry, 1篇Dalton Transactions, 1篇Crystal Growth & Design, 1篇European Journal of Inorganic Chemistry。其中1篇论文被Inorganic Chemistry选为封面文章发表，主要研究成果被著名的微信公众号X-mol推送介绍。