杯芳烃修饰的金、银纳米团簇的制备及性质研究

Metal nanoclusters have been of great interest due to their diverse structures and interesting properties. Synthesis and characterization of functional metal nanoclusters is one of the most important issues in cluster chemistry. The objective of this project is to use macrocyclic ligands such as calixarenes for the stabilization of new functional gold/silver nanoclusters. Firstly, the preorganized calixarene is selected and reacts with gold/silver precursors via the direct reduction method or ligand exchange post-modification strategy, to afford diverse calixarene-protected gold/silver nanoclusters and increase the stability of these clusters, in propose to realize both synthetic control and structural characterization. Secondly, modulating the properties of nanoclusters by integration of host-guest interaction features of calixarene with optoelectronics, catalytic properties of nanoclusters; investigating the structure-property relationships of the systems and also exploring the potential applications such as host-guest recognition, ion detection, and catalysis.

金属纳米团簇的结构复杂，功能丰富，备受关注。纳米团簇的结构表征和功能化是团簇化学中的重要难题。本项目提出以具有大环结构的杯芳烃为表面保护配体制备多功能化的金、银纳米团簇。拟设计预组织化的、易修饰的杯芳烃配体和各类金、银前驱体反应，以直接还原法和配体交换后修饰法的合成策略，获得结构多样性的杯芳烃保护的金、银纳米团簇，并提高团簇的稳定性，实现纳米团簇的可控制备和结构的精确表征；对团簇进行功能化，将杯芳烃的主客体识别特性和团簇的光、电和催化性质有机地结合，深入研究其物理化学性质，揭示结构与性能关系，并应用于主客体分子识别、离子检测、催化等方面。

纳米团簇的结构表征和功能化是团簇化学的重要目标。本项目开展以下三方面工作：(1)发展了一种大环修饰的纳米团簇的合成新方法，实现了杯芳烃保护的金、银纳米团簇的可控制备和结构的精确表征，发现了大环配体兼具稳定性和灵活性的独特优势，探索了借助超分子作用力调控团簇的结构和性质；(2)开展了异核金属团簇的设计合成，研究了团簇的原子排布、电子结构和表界面特性，通过强键规则、异核规则以及理论计算合理解释了团簇稳定性增强的本质，为团簇的性能开发和应用提供基础；(3)团簇被认为是纳米颗粒和小分子的桥梁，项目分别从以团簇为基元来组装聚合物和单核/双核金属杂环配合物的合成和反应性这两个方向对课题做了有益的延伸探索。通过本项目资助共发表SCI论文8篇，其中JCR一区论文4篇，含Angew. Chem. Int. Ed.、 Chem.Sci.、Chem. Comm.等。