可调控的功能性水相超分子聚合物的构建及性能

Functional dyes, such as fluorophores (like Aggregation-Induced Emission groups), room temperature phosphors, chiral moieties, sensing parts etc. are employed as starting guest materials. They will be well designed and integrated into various supramolecular polymers via cyclodextrin, cucurbituril and hydrophilic calixarene based host-guest recognition in aqueous solution, which makes the hydrophilic supramolecular polymers provided with fluorescent and room-temperature-phosphorscent emission, sensing specific analysts etc. Introduce photo-responsive azobenzene and photochromic diarylethene, redox-responsive viologen and pH-responsive amine etc. into guest monomers to construct stimuli-responsive supramolecular polymers. Control the assembly/dissociation between the guest parts and host moieties of supramolecular polymers. Adjust such functions as fluorescence increase/decrease, red-shift/blue-shift, chiral intensity and transition, switching between hydrogel and aqueous solution etc. Investigate the macroscopic properties of hydrophilic supramolecular polymers in non-solution media, like self-healing of their hydrogel and solid state, to develop controllable functional hydrophilic supramolecular polymeric materials.

将荧光基团（如聚集诱导发射AIE效应的基团）、室温磷光基团、手性基团、传感单元等功能染料基团引入到客体单元中，通过环糊精、葫芦脲和磺化杯芳烃等亲水性大环主体的识别作用，来构建具有相应功能的水相超分子聚合物，制备具有不同荧光发射、可以发射室温磷光信号、能识别传感特定离子客体等功能的水相超分子聚合物；将能响应外界光、氧化还原和酸碱变化等刺激的功能染料基团（如能发生光致异构化的偶氮苯和发生光致变色的二噻吩乙烯单元、能被还原然后再氧化的紫精基团和容易被酸化然后再去质子化的胺等）引入客体单元来构建水相超分子聚合物，通过各种外界刺激来调控水相超分子聚合物的组装与解离（聚合物与单体或小的超分子单元之间），调控其功能（如荧光的增强与猝灭、红移与蓝移，手性信号的强弱变化和转变，水凝胶态和溶液态之间的转换）；通过各种刺激手段来调控非溶液态超分子聚合物（如水凝胶或者固态）的自修复等宏观材料性能。

本项目旨在构建系列可调控的功能性超分子聚合物并研究其性能。构建了系列具有荧光发射，室温磷光发射，光致变色等功能的新颖的超分子及聚合物体系，并具有刺激-响应型功能，拓展并超额完成了研究目标：如构建了具有多色荧光发射响应（包括白光发射）的单一主客体超分子；发展了纯有机无定形态小分子室温磷光材料；制备了纯有机无定形态无重原子室温磷光聚合物材料；合成了具有室温磷光信号作为输出的分子梭；通过超分子协同效应的策略，实现了有机单分子白光材料的新突破；制备了纯有机高效室温磷光发射的无定型聚合物材料；发展了基于三枝状二噻吩乙烯功能化合物的光响应超分子聚合物等。在JACS，Angew，Chem Sci，Adv Opt Mater，Ins Eng Chem Res，Chem Commun和Macromol Rapid Comm等期刊上发表论文三十余篇。该项目的顺利完成丰富了光响应的超分子和超分子聚合物材料体系的构建，拓展了精细化工领域有机功能染料的新功能和应用新领域。