钌金属簇合物与过渡金属配合物功能单元的组装反应及其分子功能体系的性质

The demand for functional molecular materials is increasing rapidly in many fields. It is highly desired to precisely synthesize some molecular systems with controllable specific functions and properties. Multicomponent molecular systems containing different functional groups, especially those composed of metal complex-based building units, may display not only the original properties of each component but also some new fantastic functions due to the synergetic effects among the units. Therefore, such systems may be promising candidate materials for some molecule devices. In this work, some di- and trinuclear ruthenium complexes will be used as building units to react with the catalyst complexes based on transition metals such as Pt(II)，Pd(II), Fe(II) and Co(II), and to construct some multicomponent molecular systems. The structures and the properties of the resulting systems will be investigated. The systems showing better catalytic properties will be introduced on the solid surfaces such as gold and ITO（indium tin oxide）to fabricate orderly structures. And the properties and the applications of the resulting surface structures will be explored. On the basis of the experimental results, the reaction mechanism and the interactions among the components will be elucidated with the aid of theoretical calculations. By understanding the reaction mechanism and the interactions between the building units, we attempt to reach the point where one can synthesize some functional molecular systems precisely and tune their properties. This work will have some experimental and theoretical contributions to the development of functional molecular materials based on metal complexes.

新型分子功能材料在各领域的应用日趋广泛。实现具有特定功能的分子体系的精准合成与调控，是人们孜孜以求的目标。含不同功能基团的多组分体系，特别是以不同金属配合物作为基本单元进行混合组装而得到的一些分子系统，不仅可以表现出各功能基团的原有性质，还可能实现不同基团之间的协同作用,产生新的整体性质，因而在发展为分子功能材料方面很有潜力。本项目中，利用双、三核钌簇合物作为基本单元，与具有催化活性的Pt(II)、Pd(II)、Fe(II)、Co(II)等金属配合物组装成多组分分子体系。对组装体进行结构鉴定和性质研究。筛选性能良好的体系组装到金、导电玻璃等固体表面，制备有序的纳米结构并探索其应用性质。进行理论计算,结合实验基础，阐明体系内各基团的协同作用及其对整体性质的影响。试图通过研究配合物基本单元之间的组装机理和规律，实现多组分分子功能体系的精准合成与性质调控，为研发以金属配合物为基础的功能分子材料提供实验基础及理论依据。

用具有不同功能的单元组装成多组分分子体系，实现分子组装体的精准合成与调控，发展具有特定功能的新型分子材料，是满足社会发展对功能材料需求的途径之一。本项目中，设计合成了2,6-dpes、2,6-dppy、2,6-dppyBr、2-DTE、2-DTEL、2-dtpBr和dbes等3大系列共9个新型多齿螯合配体,分别用它们与Pt(II)、Fe(III)、Cu(II)和Co(II)等过渡金属离子反应，制备了有发光或/和催化性能的新型配合物。用这些配合物作为基本单元与具有氧化还原活性的双核钌配合物[Ru2O(CH3COO)2(AA)2(L)2]m (AA：pyridine (py)2, 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), L：a monodentate ligand)、三核钌簇合物[Ru3O(OOCR)6(L)3]n (R：aryl or alkyl, L：H2O, CO, N-heterocycles, etc.)进行组装反应，制备成Ru-Pt、Ru-Cu等多组分分子体系。测试表征了Pt(II)、Cu(II)、Co(II)等新型金属配合物以及Ru-Pt、Ru-Cu等多组分分子体系的光谱、氧化还原、催化及热稳定性等各种性质。研究了配合物以及多组分分子体系的结构与性能之间的关系，归纳总结构效规律。对实验体系进行理论计算，结合实验数据，分析探讨了多组分分子体系内不同功能单元间的电子传递、电子偶合及协同效应机制。在导电玻璃、碳材料等固体表面组装Ru-Pt、Ru-Cu多组分分子体系的有序纳米结构，并研究其光学、催化性质。发现配体本身的氧化还原性质及侧链取代基对配合物的催化性能有重要的影响。合成的有些配体及铂配合物是良好的化学传感器。实现了利用钌配合物单元的氧化还原性质对铂、钴、铜等配合物单元的光学/催化性质进行调控。此项目的研究结果为研发基于金属配合物分子组装体的功能分子材料提供了实验基础及理论依据。