具有自愈合性能的稀土配合物杂化发光材料的超分子构筑

The project will focus on self-healable lanthanide complex-based organic-inorganic hybrid materials of highly efficient luminescence prepared under aqueous conditions. Novel positively charged lanthanide complexes will be designed and synthesized, which are soluble and can self-assemble into spherical micelles showing sufficient luminescence in water. The amphiphilic micelles will be used as effective and luminescent “molecule binder” to the exfoliated nanosheets precoated with sodium polyacrylate into networks via electrostatic interactions, producing lanthanide complex-based organic-inorganic hybrid materials with good mechanical properties, fast self-healable ability and high luminescence efficiency. In this project, we will explore prepare procedure and the mechanism responsible for the formation of the luminescent self-healable materials, study luminescent properties and self-healing ability, and investigate luminescence mechanism and self-healing mechanism. This project will realize the simple and fast preparation of self-healable and highly luminescent lanthanide complex-based organic-inorganic hybrid materials under aqueous conditions, provide data and technology for the application of lanthanide complex-based organic-inorganic hybrid materials in fabricating flexible optoelectronic device.This study is of high importance for developing new preparation strategy and procedure for obtaining new multifunctional materials. Furthermore, it can also help us make use of lanthanide-based materials in new and high technological fields as well as convert the advantages of lanthanide resource to economical and technological ones.

本项目致力于在水环境中制备具有快速自愈合性能的高效配合物杂化发光水凝胶。设计合成带正电荷的新型稀土发光配合物，它们在水溶液中能够自组装为表面带正电荷的高效发光胶束；采用该稀土配合物胶束作为功能“分子胶水”，通过静电相互作用将在水中均匀分散的粘土纳米片层交联形成网络结构，制备出机械强度高、自愈合速度快、发光效率高的稀土杂化发光材料。探索制备规律和材料的形成机理，研究发光性能和自愈合性能，考察其发光机理和自愈合机理。本项目能够赋予稀土配合物杂化发光材料以快速自愈合性能和实现水环境下新型高效稀土配合物杂化发光材料的制备，为稀土配合物杂化发光材料在柔性智能光电器件中的应用提供技术和材料支持，同时也有助于开辟稀土高技术应用新领域，并进而将我国稀土资源优势转化为经济和技术优势。

本项目主要开开展了如下工作：1）设计合成了一系列含三联吡啶基团或吡啶二羧酸基团的新型有机配体，它们能与稀土离子形成发光配合物; 将所合成的有机配体与稀土离子（主要为Eu3+和Tb3+）或稀土配合物 （如，稀土b-二酮配合物、稀土吡啶二甲酸配合物等）配位，制备出了系列发光稀土有机配合物。2）将特定有机配体、稀土离子（或稀土有机配合物）与纳米黏土颗粒或/和高分子材料自组装为具有自愈合特性的发光水凝胶和发光薄膜等发光材料，阐明了相关自组装机理和自愈合机制。3）水溶液中将Eu3+-L配位聚合物和具有光致变色功能的DAE 分子（OF形式，即开环形式）按一定比例混合，得到超分子组装体，组装体的颜色和发光颜色对特定波段的光具有快速响应性，表现出优异的可逆光开关性能。4）采用端基被配位基团（如三联吡啶）所修饰的高分子与稀土离子配位的策略，制备出了系列既具有良好的机械强度和弹性又具有快速自修复特性的稀土聚合物发光材料。本项目的研究提供了系列新型稀土配合物和刺激响应型的自愈合稀土发光材料及其制备技术，为稀土发光材料在柔性智能光电器件中的应用提供了材料基础，有助于将我国的稀土资源优势转化为技术优势。在Nature Communication, Angewandte Chemie International Edition, Advanced Science, Chemical Engineering Journal 等权威刊物上发表SCI收录论文35篇，申请国家发明专利4件。