多模式轮烷分子机器的合成及其自组装

This project aims to construct a series of novel multi-mode-driven rotaxane molecular shuttles, in which several functional units with excellent electronic/optic properties are integrated. In this kind of multi-functional molecular systems, multi-mode regulation of intercomponent interactions, such as electron transfer and energy transfer processes between functional units can be achieved in response to external stimuli, accompanying remarkable changes in the output signals, such as fluorescence and color changes. In this kind of rotaxane molecules, substituted stilbene or azobenzene moieties will be introduced into the dumbbell-shaped molecules of the rotaxane systems and situated between the two different recognition sites. The photoactive units can function as "brake" units and can be used to manipulate the movement of the macrocycle component between two recognition sites. This kind of rotaxane molecular shuttles can be utilized to construct novel-concept functional molecular systems, such as adjustable multi-stable molecular switches, bi-directional molecular locks and molecular sequential logic devices. A series of anchoring groups will be introduced into the stoppering parts of chemically driven molecular shuttles that feature excellent electronic and optic properties. These modified rotaxanes with anchoring groups will be immobilized into the surfaces of Au electrode, quartz or glass to form self-assembled monolayer, which can increase the space for molecular motion of the rotaxane-type molecular machines. The investigation of the coordinated and synergistic movements of molecular machines in self-assembled monolayer and the influences of the movements to the physical properties of the interfaces, can provide fundamental basis for the development of novel functional self-assembly systems and novel micro-fluidic devices.

本研究创新构建新型多模式轮烷型分子机器体系，将多个具有光电活性的功能分子单元集成到同一轮烷体系中，在外界刺激组合下多模式调控轮烷体系各功能基团之间的电子、能量转移等相互作用，并能带来体系荧光、吸收等可肉眼识别信号的显著变化；在轮烷杆状分子的两个识别点之间引入光异构化二苯乙烯或者偶氮苯等作为"闸"单元，利用"闸"来操控环状组分在两个识别点间的运动，构建可调控的多稳态分子开关、双向分子锁、分子时序逻辑等新概念功能体系；筛选性能优异的酸碱控轮烷型分子机器体系，对这些轮烷分子的端基进行合理的修饰，利用自组装的方法等方法将其固载到金电极、石英或者玻璃表面，来增大分子机器运行空间，研究分子机器在界面的协同运动以及运动过程对界面物理、化学性质的影响，为发展新型的功能自组装体系和发展分子机器的微流体器件打下基础。

刺激响应性多模式、多平台分子机器的设计与合成是目前有机合成化学与超分子化学以及分子机器领域的研究热点。本研究创新设计并构建新型多模式驱动的轮烷型分子机器体系，将多个具有光电活性的功能分子单元，例如二茂铁、分子转子等功能基团集成到同一轮烷体系中，在外界刺激组合下多模式调控轮烷体系各功能基团之间的电子、能量转移等相互作用，并能带来体系荧光、吸收等可肉眼识别信号的显著变化，并用来构建可调控的多稳态分子开关。设计并合成了一系列端基修饰的轮烷型分子梭，将其组装到二氧化硅纳米颗粒上以及聚合物侧链上，为研究分子机器在界面的协同运动以及运动过程对界面物理、化学性质的影响提供了研究对象，为发展新型的功能自组装体系和发展分子机器的微流体器件打下基础。另外，研究了一系列功能超分子基元的可控组装行为，创新的实现了光控可逆超分子聚合物的切换。实现了无机半导体二氧化钛纳米颗粒的双模式可控组装、解组装，将其用于可转化的光催化剂。在基金支持下，以通讯作者或者第一作者发表已发表SCI论文29篇，受邀在国际学术会议上作分会报告2次、全国会议分会报告3次，培养博士、硕士多名。