基于螺烯的手性自组装及手征性光学性质研究

Chiral materials show promising prospect in many fields such as catalysis, pharmaceutics and informatics. Helicene is a type of special chiral molecules with distinctive chiroptical properties. However, recent works mainly focus on the molecular level, while it still remains challenges in how to assembly helicene using supramolecular interaction to construct more outstanding chiroptical materials with more variety. In this project, a series of helicene derivatives possessing specifically functionalized groups are synthesized. By intermolecular non-covalent interactions, the helicene derivatives can reach flexible and controllable self-assembly, forming novel 1D or 2D chiral nanostructure, and the stacking forms can vary by careful design of molecular structures and experimental factors. By studying and concluding the relation between the self-assembly morphology and the we can reach the continuous, accurate and reversible tuning of chiroptical properties in supramolecular level, and furthermore build up devices such as supramolecular chiroptical switches, and also explore the application of these self-assembly materials in circularly polarized luminescence and catalysis. This project is expected not only to explore the principle of helicene-based self-assemblies, enrich the structuring tactics for self-assembly, but to provide innovative idea for developing novel chiroptical materials and devices also.

手性材料在催化、医药、信息等领域具有重要的应用前景。螺烯是一类特殊的手性分子，拥有优异的手征性光学性质，但目前相关方面的研究工作主要局限于分子层次，如何将螺烯分子通过超分子作用相互组合起来，构建性能更为丰富、突出的手征性光学材料，仍然十分具有挑战性。本项目拟合成一系列含特征功能化基团的螺烯化合物，通过螺烯分子间的非共价作用实现灵活、可控的有序自组装，形成一维、二维等新型手性纳米结构体。通过对分子结构与实验参数的细致设计，诱导螺烯砌块以不同方式堆叠，系统研究自组装结构形态与手征性光学性质之间的联系，总结规律，实现手征性光学性质在超分子层次上的的连续、精确、可逆表达，由此构建手征性光学超分子开关等器件，并探索这类自组装材料在圆偏振发光、不对称催化等领域的应用。本项目旨在探索螺烯类新砌块的自组装机制，进一步丰富手性自组装的构建策略，为研发新型手征性光学材料与器件提供崭新的设计理念。

手性材料的聚集与组装在诸多领域有着十分重要的意义。本项目利用螺烯的特殊螺旋共轭结构，通过超分子作用将其相互组合起来，构建开发了一系列性能丰富、突出的手征性光学材料。例如，本项目合成了一系列具有长臂结构的螺烯化合物，利用螺烯之间的相互手性作用，构筑了具有三维螺旋纳米结构的手性分子笼，由此开发出手性客体响应性手征性光学材料；合成了一系列具有聚集诱导发光基元的螺烯衍生物，利用调控其聚集行为系统研究了手性结构形态与手征性光学性质之间的联系，从而构建出性能优异的聚集诱导圆偏振发光材料；通过螺烯衍生物与DNA相互结合，探索了手性-手性超分子相互作用的机制，实现手征性光学的连续、精确、可逆表达，最终实现了高效可调的圆偏振发光。综上所述，本项目利用螺烯衍生物在聚集组装领域上的探索，为手性自组装提供了新的构建策略，也为新型圆偏振发光材料的设计提供了崭新的设计理念。