基于六苯并蔻的形状两亲化合物的合成、自组装与性能研究

Properties of materials are not only closely correlated with their chemical structures but also strongly influenced by the self-assembled hierarchical structures of the molecules. Possible to form complex hierarchical structures, shape amphiphiles have attracted a lot of attention. One of the objectives of this proposed project is to synthesize several series of chemically precisely defined shape amphiphiles containing hexa-peri-hexabenzocoronene (HBC) as the disc-like component owing to its excellent charge carrier mobility. The molecular design will combine symmetry breaking and size matching. The other component in the shape amphiphiles will be a rod-like segment or a banana-shaped molecule. The self-assembling behaviors of the shape amphiphiles in bulk and in thin films will be systematically investigated by a combination of structural analysis, thermal analysis, microscopy, and other modern analytical techniques to reveal the impact of shape parameters, coupling/decoupling effect, chirality, and blending of composing units on the self-assembled structures. External fields such as electric field and magnetic field will be utilized to control the structure and the orientation of the self-assembly. With consideration of the functionalities of the composing units, the relationship between the properties (such as semiconducting and ferroelectric/antiferroelectric properties) and the structures (both chemical and self-assembled structures) of the shape amphiphiles will be established, and the preparation of new functional materials will be explored through a “bottom-up” approach. This project will lead to research works with significant impact in the international scientific community as well as creative research achievements with our own rights of intellectual property.

材料的性能不仅与其化学结构密切相关，分子在不同尺度的组装结构也有着重要影响。形状两亲分子作为一类可以形成丰富多级有序结构的分子而受到极大关注。本项目旨在结合对称性破缺和尺寸匹配的设计理念，选取具有良好电荷传输能力的六苯并蔻（HBC）为盘状基元，合成几个系列结构明确的盘状-棒状和盘状-香蕉型形状两亲分子，利用结构分析、热分析、显微技术等多种现代分析测试技术系统地研究其在本体和薄膜中的自组装行为，揭示形状参数、耦合/去耦合效应、手性中心、组成结构单元的掺杂等因素对于形状两亲分子自组装行为的影响。同时，利用电场、磁场等外场来调控形状两亲分子的自组装结构和取向。结合形状两亲分子中结构单元的功能性，建立形状两亲分子的半导体性质、铁电性/反铁电性等性能与其化学结构、自组装结构之间的关系，进行自下向上构建新型功能材料的探索。做出一批在国际上具有重要影响的工作，并获得原创性的具有自主知识产权的研究成果。

本项目旨在结合对称性破缺和尺寸匹配的设计理念，合成几个系列结构明确的盘状-棒状和盘状-香蕉型形状两亲化合物，系统地研究其在本体和薄膜中的自组装行为和结构-性能关系，揭示形状参数、手性中心、组成结构单元的掺杂等对于形状两亲分子自组装行为的影响，进行自下向上构建新型功能材料的探索。本项目取得的主要成果有：（1）制备了多种形状两亲分子，并获得了多种多级自组装结构；（2）揭示了体系中多种相互作用对形状两亲分子相行为的影响规律，实现了对自组装结构和尺寸的控制；（3）阐释了形状效应及对称性破缺对手性在不同尺度上的传递规律，阐明了观察到的宏观螺旋结构的形成机理。

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