8-羟基喹啉类多核金属配合物的组装、结构和发光性能研究

Owing to the collaborative multifunctionalities, tunable structures and properties, metal-organic luminescent complexes have received considerable attention in the past decades. Herein, a variety of 8-hydroxyquinolinate-based organic ligands with different sizes, charges, geometries and functions will be designed and synthesized. Based on the principle of coordination and supramolecular chemistry, various novel multinuclear crystalline complexes (such as metal-organic clusters and multinuclear cage with internal cavity) with good fluorescent properties will be fabricated, and their fluorescent properties (emission wavelength, fluorescent lifetime and quantum yield and so on) will be explored in the solid state and solution. A special emphasis will be given to study the tuning of fluorescent properties through introducing functional groups, changing the core structures, controlling the supramolecular packing characteristics and guest molecules. In this way, some novel multinuclear crystalline materials with tunable emission wavelength and high fluorescent quantum yield can be obtained. Their applications in the recognition of functional organic molecules (such as amino acids, nucleotides, saccharides and so on) and organic light-emitting diodes (OLEDs) will be further investigated. Finally, we will extensively study the influence of synthetic methods, steric and electronic features of building units on structures of 8-hydroxyquinolinate-based multinuclear complexes, and the relationship between structures and properties. All the efforts will help us to further synthesize novel crystalline luminescent materials with potential applications.

金属-有机发光配合物具有功能复合、结构与性能可调等优点，是近年来深受重视的一类多功能分子基材料。本项目拟以8-羟基喹啉骨架为平台，设计合成多种长度、电子和立体结构、功能不同的多齿桥联配体，基于配位化学和超分子化学原理，构筑各种具有新颖的多核结构并兼具良好荧光性能的晶态配合物（如多核簇合物、含内部空腔笼状多核结构等）。深入研究这类多核配合物在固相及溶液中的荧光性能（发光波长、荧光寿命、荧光量子产率等），重点探索功能基团、核结构、空间堆积和客体分子等手段调控多核配合物的荧光性能，筛选出多种发光波长可调和荧光量子产率高的多核配合物，考察其在功能小分子识别（如氨基酸、核苷酸和糖等分子识别）和电致发光器件两方面的应用。总结8-羟基喹啉基多核配合物的组装方法、组分的空间和电子结构与材料结构的关系，以及材料结构与发光性能之间的关系，为进一步指导合成具有良好应用前景的新型发光材料奠定基础。

本项目基于8-羟基喹啉骨架，合成出系列具有不同结构和功能的8-羟基喹啉配体，其与金属离子配位组装出系列不同结构类型的8-羟基喹啉类多核晶态配合物，发展了这类发光材料的合成方法学。深入研究多核金属配合物的发光性能，并且根据其结构和功能特性，系统开展了发光配合物在OLED器件、荧光检测分子/离子等方面的应用研究。主要在以下几方面取得系列研究成果：（1）8-羟基喹啉基多核主族金属配合物的组装及其OLED器件性能研究；（2）8-羟基喹啉基多核过渡金属簇合物的组装及其发光与糖分子识别性能研究；（3）8-羟基喹啉基多核金属-有机笼的组装及其性能研究；（4）8-羟基喹啉基金属-有机框架的组装及其荧光识别分子/离子性能研究。系统研究了8-羟基喹啉基多核金属配合物结构与发光性能之间的关系，为今后可控制备具有特定结构和功能的多核金属-有机配合物提供了理论和实验依据。作为本项目标注的研究成果，已在Chem. Commun., Inorg. Chem., Inorg. Chem. Front., Coord. Chem. Rev.等杂志上发表高质量SCI论文7篇。