多金屬氧簇復合物體系的可逆動態組裝、可控光致變色及超分子催化研究報告

摘 要：分子自組裝是分子自發形成特定有序聚集結構的過程。為了建立新的功能自組裝體系，實現分子聚集體由單組分到多組分、由靜態到動態，并通過環境變化進而實現從聚集體結構可控發展到功能可控，在過去一年里，我們從無機金屬氧簇和與之匹配的有機組分構筑基元設計入手，通過組分間結構匹配和作用方式、組裝性質、刺激響應及功能特性調節，合成了一系列新的以無機簇陰離子為核、以修飾的有機陽離子為殼的雙組分通過靜電相互作用形成的、具有刺激響應性和適應不同功能需要的、結構形態可變的兩親性超分子復合物預組裝體。我們以研究復合物自組裝形成的多級聚集結構為基礎，通過揭示響應基團與組裝結構間的聯動關系，獲得了具有可逆轉變特性的分子組裝體并闡明了動態轉變過程和機理。在此基礎上，我們利用溶液中組裝結構的動態可調控特性，通過光照和溫度變化調控分子間相互作用，實現了水相中分子聚集體的組裝與解組裝、極性相和非極性相之間的可逆相轉移、可逆氧化還原和相轉移催化氧化功能。該年度的工作實現了將有機和無機組分通過多種相互作用整合到同一個組裝體系中，揭示了多金屬氧簇超分子復合物的手性轉移和可逆光致變色、手性組裝結構與非手性組裝結構的動態結構可逆轉變和機理，同時實現了同時含有主體和客體基團的超分子復合物自識別、手性轉移和手性放大的光調控。這些工作將為實現該研究的下一步目標提供很好的基礎。

關鍵詞：有機-無機復合體系 自組裝 分子聚集體 動態調控 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 controllable characteristics of assembled structures， through adjusting the molecule interaction by temperature and light in solution， and finally realize phase transfer， redox and catalytic oxidation of assemblies under mild conditions. The job of this year integrates various components in one assembly system through multiple interactions. We uncovered chiral transfer and reversible photochromism， reversible transformation of helical and spherical assembled structures and the possible mechanism. Meanwhile， we have realized the photo-modulation for the self-recognization， chiral transfer and amplification of dynamic reversible self-assemblies of an inorganic/organic complex bearing host and guest simultaneously. All the present research results pave the strong base for the realization of the next targets.

Key Words： Organic-Inorganic Complex system； Self-Assembly； Molecular aggregation； Dynamic control； Function

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