稀土聚合物凝胶的设计组装及光化学传感性质研究

Rare earth is one of the important strategic resources in China, and the research on functions and application technologies of rare earth compounds constitute an important research topic in the 21st century. In this project, dynamic reversible coordination placed first and effects of other non-covalent bonds second, rare earth ions or rare earth complexes were imported into functional polymer gel system so as to realize their flexible and controllable assembly and recombination at micro-nano layer in 3D spatial gel network, expecting to obtain gel-state rare earth polymer materials with dynamic reversible structure, superior mechanical properties, self-repairing performance and visual photochemical sensing properties. On this basis, a systematic study of synergistic assembly mechanism and dynamic driving behaviors between rare earth material and polymer molecules was conducted; optical behaviors and energy transfer mechanism between gel-state rare earth material and gel molecules were further discussed; a new identification mechanism with multiple sites and multiple synergistic effects was designed, and then rare earth polymer gel with high sensitivity, high selectivity and strong reversibility to environmental species was constructed. This research will provide a new design idea for development of new-type multi-functional rare earth materials so as to expand the range of application and practice of rare earth materials.

稀土是我国重要的战略资源之一，稀土化合物功能和应用技术的研究是21世纪化学的重要课题。本项目拟以动态可逆配位作用为主，其他非共价键作用为辅，将稀土离子或稀土配合物引入到功能聚合物凝胶体系中，在三维空间凝胶网络中，实现它们在微纳米层次上的灵活可控组装与复合，以期获得结构动态可逆，具备优异力学性能、自修复性能和可视化光化学传感性能的稀土聚合物凝胶态材料。在此基础上，系统研究稀土材料与聚合物分子间的协同组装机制和动态驱动行为；深入探讨凝胶态下稀土材料和凝胶分子间的光学行为和能量转移机制；设计多位点、多协同作用识别机制，构建对环境物种具有高灵敏度、高选择性、可逆性强的稀土聚合物凝胶。该研究将为新型多功能稀土材料的开发提供新的设计思路，从而拓宽稀土材料的应用和实用范围。

稀土聚合物凝胶材料同时具有类固体的粘弹性和修复性，还具有溶液的均一性，易于形变，均匀性强，便于实际运输及泵抽或注射取样。此外，聚合物凝胶尤其是水凝胶，可对外界刺激做出快速、灵敏的响应和多重信号表达，在形状记忆材料、自修复材料、生物组织工程、光电和智能材料等领域都有重要的应用。.在本项目中，基于共价键聚合、超分子组装和配位化学基本原理，利用有机合成和分子工程技术的方法，设计了一系列基于三联吡啶类有机配体的新型的具有优异光学性能、力学性能、传感性能和自修复性能的稀土聚合物凝胶。系统研究了材料的光学、力学性质，及分子结构和宏观性能间的构效关系；探讨了稀土聚合物凝胶对外界刺激的响应机制。该研究为新型多功能稀土材料的开发提供了新的设计思路，为该类材料在发光材料、有机物检测等领域的广泛应用提供基础性研究数据及理论指导。