刺激响应性轮烷分子的制备及其表界面自组装性能研究

It’s a necessary way to make the research of molecular machines from solution to solid state or quasi-solid state to achieve its deviceization and materialization and it’s also a challenging and important issue to immobilize it on the surface and maintain high-efficient operation efficiency. In this project, we intend to synthesize a series of stimuli-responsive rotaxane molecular systems with novel structures or functions. And then through three covalent attachment points, the azide-functionalized background ligands and the alkynyl-functionalized rotaxane molecules are immobilized on the surface interface by covalent bond to form an ordered self-assembled monolayer to enhance the stability of the surface interface molecules. The large specific surface area of the material system and the effective space provided by the partially unreacted background ligand ensure sufficient free space for the functional rotaxane molecules to operate stably. In the quasi-solid state environment, the microscopic motion of the self-assembled monolayer achieves integration and amplification through changes in the macroscopic properties of the material interface. The material properties show stimuli responsiveness to changes of the external environment, such as the inclusion and controlled release of dye molecules, and the change of surface wettability, which lays the foundation for the deviceization and materialization of molecular machines.

人工分子机器的研究从液态过渡到固态或准固态是实现其器件化和材料化的必经之路，如何将其固载到表界面并保持高效的运转效率，这是一个有挑战且有重要意义的课题。本项目拟合成一系列新颖结构或功能的刺激响应性轮烷分子体系，然后利用三个共价连接点将叠氮功能化的背景配体和炔基功能化的轮烷分子以共价连接的方式固定在表界面形成有序自组装单分子层，增强表界面分子的稳定性。材料体系大的比表面积和部分未反应的背景配体提供的有效空间，保证功能轮烷分子稳定运转有充足的自由空间。在准固态环境中，自组装单分子层的微观运动通过材料宏观性能的改变实现集成与放大。材料性能表现出对外界环境改变的刺激响应性，例如染料分子的包结与可控释放、表界面润湿性能的改变等，为分子机器的器件化和材料化研究奠定基础。

在该项目的支持下，研究团队聚焦功能轮烷分子的制备及其自组装性能开展研究，探索了新型功能轮烷分子在超分子聚合物和表界面自组装领域的应用，为今后拓展可能的应用奠定了基础。取得主要成果如下：1，将二茂铁和萘酰亚胺荧光团功能化的机械互锁[1]轮烷分子梭引入到聚合物领域，制备酸碱响应性线性-环形结构可控智能超分子聚合物；2，基于柱[5]芳烃与中性氰基客体的主客体识别作用，设计合成柱[5]芳烃桥连的四苯乙烯和氰基结构功能化的AB型单体分子，其在溶液中自组装形成超分子聚合物进一步聚集成具有AIE效应的球形聚集体，构建具有聚集诱导效应的超分子聚合物；3，利用双亲性轮烷分子的刺激响应性，将其固载到玻璃表界面，研究其在外界刺激下的可控润湿性能，构建表界面润湿性能可控的智能响应性功能材料。该项目的实施对于拓展轮烷分子的应用，构建智能响应性功能材料具有重要的科学意义。