多金属氧簇复合物体系的可逆动态组装、可控光致变色及超分子催化研究报告.docVIP

多金属氧簇复合物体系的可逆动态组装、可控光致变色及超分子催化研究报告 　　摘 要：分子自组装是分子自发形成特定有序聚集结构的过程。为了建立新的功能自组装体系，实现分子聚集体由单组分到多组分、由静态到动态，并通过环境变化进而实现从聚集体结构可控发展到功能可控，在过去一年里，我们从无机金属氧簇和与之匹配的有机组分构筑基元设计入手，通过组分间结构匹配和作用方式、组装性质、刺激响应及功能特性调节，合成了一系列新的以无机簇阴离子为核、以修饰的有机阳离子为壳的双组分通过静电相互作用形成的、具有刺激响应性和适应不同功能需要的、结构形态可变的两亲性超分子复合物预组装体。我们以研究复合物自组装形成的多级聚集结构为基础，通过揭示响应基团与组装结构间的联动关系，获得了具有可逆转变特性的分子组装体并阐明了动态转变过程和机理。在此基础上，我们利用溶液中组装结构的动态可调控特性，通过光照和温度变化调控分子间相互作用，实现了水相中分子聚集体的组装与解组装、极性相和非极性相之间的可逆相转移、可逆氧化还原和相转移催化氧化功能。该年度的工作实现了将有机和无机组分通过多种相互作用整合到同一个组装体系中，揭示了多金属氧簇超分子复合物的手性转移和可逆光致变色、手性组装结构与非手性组装结构的动态结构可逆转变和机理，同时实现了同时含有主体和客体基团的超分子复合物自识别、手性转移和手性放大的光调控。这些工作将为实现该研究的下一步目标提供很好的基础。 　　关键词：有机-无机复合体系 自组装 分子聚集体 动态调控 功能 　　Abstract： Molecular self-assembly is the process that molecules or molecular groups spontaneous form specific aggregation structure. New functional self-assembly systems with the molecular aggregations changing from monocomponent to multicomponent， from static structure to dynamic evolution， and from structural control to functional adjustment， through the stimulus of outside environment， have now become challenges and the coming goals. To match the purpose of the present project， we start to design new type of building block bearing inorganic polyoxometalate clusters and organic functional units. Through the regulation of matched structures and interactions among these components， the dynamic assembly and stimuli-response properties are investigated by variable shape and amphiphilicity of the supramolecular complexes which contain inorganic clusters as the core and surface modified organic cations as the shell. From the obtained multilevel aggregation structures constructed by the self-assembly of the complexes， we demonstrate the relationship between responsive groups and assembly structures. Following these understanding， we achieve dynamic assemblies with reversible transformation characteristics， and further identify their transformation process and mechanism. On the basis of this， we have taken advantage of dynamic con