膦酸构筑的高核Ag-M杂金属簇的合成、结构与性能

Metal cluster compounds have attraction great attention due to their diverse structures and interesting properties. The project focus on the high-nuclearity of Ag-M heterometallic clusters constructed with phosphonates based on the former study, and studies the formation process and catalytic, luminescent and magnetic properties of high-nuclearity heterometallic clusters, understands realizes both structural control and properties modulation. The work includes aspects such as: (1) assemblying the silver(I) clusters and metal clusters (including main group, transition, lanthanide metals) with phosphonates as bridging ligands; (2) synthesizing high-nuclearity of Ag-M heterometallic clusters with different template anions and attaining the stability of these clusters; investigating the structure-property relationships of the systems; (3) investigating the relationships of metallophilic interactions and coordination bonds through further study of their physical and chemical properties; optimizing the properties of these heterometallic clusters. In a world, the project is essential to explore novel crystalline materials with possible applications, which possesses very important scientific significance.

金属簇合物以其结构复杂性和功能多样性而引起人们广泛关注。本项目将在完善前期研究的基础上通过膦酸来构筑高核Ag-M杂金属簇合物，探索高核杂金属簇合物的合成与组装规律，研究其催化、光学和磁学等性质，揭示其作用机制并实现有效的“结构-性能”关系调控。具体包括：(1)以有机膦酸作为桥连配体，将高核银簇分别与主族、过渡以及稀土金属簇结合起来，构筑功能化的高核杂金属簇合物；（2）探索阴离子模板对杂金属簇合物结构的调控，在获得高核杂金属簇结构多样性的同时，提高核杂金属簇的稳定性；（3）深入研究高核杂金属簇的物理化学性质，揭示亲银作用与配位键的均衡、转化和传递规律，实现性能的优化和调控。该项目将为新颖功能晶体材料的探索和应用打下基础，具有十分重要的意义。

高核金属团簇以其结构复杂性和功能多样性而引起人们广泛关注。本项目实现了膦酸构筑的高核Ag-M杂金属簇的可控合成和定向组装，明确了膦酸构筑的高核Ag-M杂金属簇合物的晶态结构及性能的关系及其调控机制。另外，在本项目的基础上，我们探索了外围配体、模板离子、电子结构和金属离子等因素对于金属团簇结构和发光性质的调控：选取不同配位能力的辅助配体，系统研究了外围辅助配体对银纳米团簇结构的调控；引入不同大小的模板离子，构筑不同尺寸的银团簇，研究其荧光性能的变化；通过还原法，制备混合价态的银纳米团簇，研究其电子结构及发光性能；在研究银团簇的基础上，进一步探索了铜团簇及其多维结构的构筑。该项目将为新颖功能晶体材料的探索和应用打下基础，具有十分重要的意义。