大分子的精细结构差别（比如立体构型）对其组装的影响是一个非常重要的主题，但目前研究较少。本项目拟将多面体寡聚倍半硅氧烷（POSS）作为模型体系，发展选择性合成方法，严格控制其表面官能团的立体构型，在此基础上制备相应的巨型分子立体异构体，并以其本体组装为例，通过系统绘制其组装相图，阐明立体构型对于巨型分子自组装结构和相行为的具体影响，并探索潜在的非传统有序结构（如Frank-Kasper相态），以此归纳和总结这些相态在巨型分子中出现的规律及分子机理，增进对于构效关系的理解，具有重要的理论和实践意义。

The fine effect of subtle structural difference (such as regio-chemistry) in macromolecules on their self-assembly is an important, yet less explored subject. The goal of this proposal is to investigate the detailed influence of three-dimensional (3D) configuration on the final self-assembled structure of giant molecules. We will use T8-polyhedral oligomeric silsesquioxane as a model scaffold and develop regio-selective methods to synthesize various regio-isomers with mixed functional groups whose distribution on the surface is precisely defined. Giant molecules will be prepared from these series of regio-isomers and their self-assembly will be studied in detail. The phase diagram relating the phase structure to its 3D configuration and volume fraction will be drawn to illustrate the effect of 3D configuration on self-assembly. Meanwhile, we also anticipate the formation of unconventional phases such as Frank-Kasper phases in some of these regio-isomeric giant molecules whose study would help clarify the underlying principle for its existence and the formation mechanism. The correlation of the phase structure with regio chemistry will improve our understanding on their structure-property relationship.