智能响应荧光币金属配合物的结构设计、合成及构效关系研究

The highly ordered crystalline materials constructed from d10 coin-metal ion (or more metal cluster units) with conjugated organic ligand have found their important niches in broad applications such as fluorescence, adsorption, catalysis, etc, and is a research hotspot in the field of chemistry and materials. This project will aim to design and synthesis of stimuli-responsively luminescent coordination complexes and relationship between stimuli-responsive functions and structure. To realize the intelligent change of luminescence behaviors, we will integrate the d10 coin-metal ions with the versatile coordination configurations and the organic ligands with conjugate  system into one highly ordered crystalline coordination complex with rich metallophilicity and using it as stimulated site if a variety of external stimuli (such as temperature, pressure, solvent molecules fumigation, etc.) are available. We will not only elucidate the intrinsic relationship between the crystal structures and stimuli-responsive functions but also explore its application in fluorescent sensor and detection to realize the rational design of new type of intelligent stimuli-responsive luminescent materials. At last, we will obtain a series of intelligent luminescent materials with the advanced functions such as sensing and detecting.

由d10币金属离子（或多金属簇单元）与具有共轭体系的有机配体组装而成的有序晶态材料在荧光，吸附，催化等方面有着广阔的应用前景，是当今化学和材料领域研究的热点。本项目将致力于受激响应的荧光功能配合物的设计合成及其应变功能与结构间关系的研究。以配位构型多变的币金属离子和具有共轭体系的有机配体组装出含有亲金属作用的高度有序的晶态配合物，以金属•••金属作用单元为受激应变位点，施以多种外界刺激（如温度、压力、溶剂小分子熏蒸等）实现荧光行为的智能变化，获得一批具有荧光传感和探测等先进功能的动态响应智能发光材料。阐明配合物晶体结构与应激响应行为间的内在关系，探索其在荧光传感器和探测方面的应用，实现新型智能响应荧光配合物的合理设计，合成及应用。

在本项目的四年执行期内，我们围绕着银基智能响应币金属配合物的合成及构效关系开展研究工作，项目期内我们合成得到了十多个具有智能响应特性的币金属配合物体系，并对它们的结构化学、合成方法、构效关系开展了详细的研究。建立了多种银基配合物的普适性合成策略，如原位阴离子模板和几何多面体规则；将高分辨质谱引入复杂配位组装体系，建立了对复杂配合物组装过程的分析策略，确认了几个团簇化合物的组装机理，并反馈优化了相关体系的合成方法。执行期内共计发表相关SCI学术论文40余篇，其中包含PNAS, JACS, Angew, Nature Comm等高水平论文11篇，部分化合物作为低温荧光温度计的材料展现了潜在的应用价值。在本项目的支持下，项目主持人成功申请到2018年国家自然科学基金委优秀青年基金项目，为进一步聚焦团簇化学研究方向，凝练团簇化学领域关键科学问题，进一步推进团簇化学的前进打下坚实基础。