d10过渡金属簇合物的设计合成及其发光性能的研究

The d10 transition metal clusters are known to present a great variety of structural forms associated with plenty types of electronic transfers, which results in excellent photophysical properties, making them widely employed in fluorescence sensing, light-emitting display and temperature detection. As the luminescent properties of d10 transition metal clusters are sensitive to the coordination modes and environment, it is still a great challenge to rationally design d10 transition metal clusters with tunable luminescent properties. The multidentate N/S-containing ligands will be selected and employed in this project. Through changing the substituent groups, coordinated atoms and coordination modes of the organic ligands, we hope obtain a series of monometallic or heterometallic d10 transition metal clusters, and explore the synthetic strategy and rules of self-assembly. In addition, we will use external stimuli such as thermal treatment, volatile organic compounds (VOC) vapors and mechanical grinding to modulate the luminescent functions of d10 transition metal clusters. The luminescent mechanism as well as the relationship between structures and photophysical properties will be investigated. This project not only expands the structures and number of transition metal clusters, but also provides some theoretical and experimental supports for further design and synthesis of the novel functional materials with tunable luminescent properties.

d10过渡金属簇合物具有丰富的结构类型和多样的电荷跃迁类型，呈现出优良的光化学和光物理性能，因此在荧光识别、光学器件及温度检测等领域应用前景广泛。这类簇合物轨道能级的分布易受晶体结构与外部环境影响，因而合成发光性能可调的簇合物材料面临极大挑战。本项目拟选用含N、S等杂原子多齿共轭有机配体，通过微调配体结构、配位原子及配位模式等构筑单一（或混合）金属簇合物，建立不同类型与结构特点簇合物的构筑策略与自组装规律；通过改变温度、有机蒸汽、机械研磨等外界条件对簇合物进行发光性能调控与优化；初步揭示簇合物发光变色机理并总结材料结构与性能之间的构效关系。本项研究不仅将拓展过渡金属簇合物的种类，而且将为合成具有光学性能可调的新型功能材料提供理论依据和实验支撑。

d10过渡金属簇合物, 作为一种无机-有机杂化发光材料，以其合成的便利性、结构的可裁剪性以及独特的光化学和光物理性能，日益在光学器件、化学传感、信息存储、生物探针等领域表现出诱人的应用前景。通过调控簇合物自组装过程的各种因素合成出具有预期结构和功能的金属簇合物，对于开发新型功能材料以及研究其结构与性能的关系，无论在理论探索上还是实用价值上都具有重要意义。本项目选用多齿刚性配体，与单一/混合d10金属离子自组装，构筑新颖的、具有高稳定性及良好发光性能的簇合物材料。探索d10簇合物的合成与自组装规律、结构与性能之间的关系；探讨不同结构导向剂、空间堆积模式等因素对金属簇合物性能的影响，并通过对以上因素的调控以期得到稳定性高、性能好的簇合物晶态材料。项目实施的过程中，我们分别采用多齿配体螯合策略和溶剂合金属离子导向策略，构筑出一系列d10单金属及异金属簇合物。通过在负电性铜碘簇基框架材料中引入三基色稀土离子客体得到长寿命纯白光发射的簇合物材料；通过引入光活性单元，使银碘簇合物实现太阳光照下降解有机物；通过引入尺寸适中模板剂，使银碘基微孔材料呈现选择性吸附及脱附性能；筛选出一例具有良好水稳定性且耐酸耐碱的锌-金属有机配位聚合物，实验证明该材料在水溶液中能够灵敏地检测Fe3+。本项目的实施为合成具有特定结构与光学性能的d10过渡金属簇合物提供思路与指导，也将为其在发光材料、荧光检测、光催化等领域的应用提供实验基础与信息。