邻菲罗啉端基化芳香型超支化聚合物的设计合成及其稀土配合物发光机理研究

The bonding-type rare earth polymer is a kind of promising photoelectric functional material by reason of the combination of the excellent properties of both rare earth luminescent materials and polymers. At present, low luminous brightness and efficiency of the photoelectric devices prepared by rare earth luminescent materials is a common problem. To solve this problem, the project develops that 1,10-phenanthroline owing excellent electron and hole transport characteristics is introduced to the molecular structures of aromatic hyperbranched polyesters having outstanding solubility, heat resistance and structural controllability. Then, 1,10-phenanthroline-end-functionalized aromatic hyperbranched polyesters can be prepared, which are used as macromolecular ligands of rare earth ions, a series of novel bonding-type rare earth polymers based on aromatic hyperbranched polyesters containing 1,10-phenanthroline end groups can be synthesized. The relationships between the molecular structures and the heat resistance, solubility and film-forming properties of rare earth polymers are studied. A thorough study of luminescent properties is carried out in order to reveal the luminescent mechanism of these rare earth polymers. A kind of new rare earth polymers owing excellent luminescent properties, processability and carrier transport characteristics is expected to be obtained by the reasonable molecular design. The studies in this project can provide theoretical guidance and experimental basis for the molecular design and preparation of high-performance rare earth polymers, and meanwhile, advance the process of rare earth polymer materials for optoelectronic applications, which is beneficial to the development and utilization of the rare earth mineral resources in our country.

兼具稀土发光材料和聚合物优点的键合型稀土聚合物是一类很有前途的光电功能材料。针对由稀土发光材料制备的光电器件普遍存在发光亮度及效率低的问题,本项目提出将具有优良载流子（电子、空穴）传输特性且为稀土离子优良配体的1,10-邻菲罗啉引入到溶解性、耐热性较好且结构可控的芳香型超支化聚酯结构中，制备邻菲罗啉端基化芳香型超支化聚酯，以其作为稀土离子的高分子配体，设计合成一系列基于邻菲罗啉端基化芳香型超支化聚酯的新型键合型稀土聚合物材料，建立起其结构与耐热性、溶解性及成膜性之间的关系，深入探讨其发光性能，揭示其发光机理。本项目通过合理的分子设计，有望获得一类具有优异发光性能、加工性能以及良好载流子传输性能的新型稀土聚合物。本项目的研究不仅会为高性能稀土聚合物发光材料的设计与制备提供理论指导和实验依据，同时有望推进稀土聚合物材料在光电领域的实用化进程，有利于我国稀土资源的开发利用。

本项目利用超支化聚合物特殊的支化分子结构以及具有较多活性端基的特点，通过化学反应将与稀土离子具有较强配位能力的邻菲罗啉结构引入到了超支化聚酯的末端，成功地获得了一种邻菲罗啉端基化芳香型超支化聚酯。进一步利用邻菲罗啉端基结构与稀土离子的配位反应制备了一系列可发射不同颜色荧光的新型超支化聚酯基稀土配合物。稀土配合物在紫外光区具有较强的吸收能力，其在紫外光激发下可发射出稀土离子的特征荧光，且超支化聚酯和第二配体的协同配位作用使其呈现出较强的荧光发射。CIE1931xy色度图分析结果表明含铕配合物发光颜色的饱和度较好，其粉末样品在365nm波长的紫外灯照射下呈现出相当强的红色荧光，且其具有相当长的荧光寿命，长达1.11ms。项目开展过程中进一步拓展了相关研究，设计合成了含三联吡啶结构和羧基结构的超支化聚酯新型配体，并制得了一系列基于该类配体的稀土配合物，其可发射出较强的不同颜色的稀土离子的特征荧光。本项目获得的具有较强荧光发射和较长荧光寿命的超支化聚酯基稀土配合物在发光显示领域具有重要的潜在应用。上述相关研究成果已申请发明专利3项，其中2项已授权，已发表学术论文3篇，在投2篇。