基于3d-4f钨-氧簇荧光材料的构筑及其稳态-瞬态发光机理研究

Luminescent materials have shown considerable promise for applications in the areas of bioimaging, solar cell, optical semiconductor, drug metabolism, information storage, biosensors, and so on. With the profound research of POM chemistry and the urgent requirement of science development, it is challengable but meaningful that the exploration of multifunctional POT-based TM-Ln heterometallic fluorescent derivatives as well as the investigation of the photoluminescence mechanism in detail which is the key points in these luminescent materials. This project focuses on design syntheses, properties and steady-transient state photoluminescence mechanisms of fluorescent functional materials based on polyoxotunstates. By the routine conventional aqueous solution method, one-pot or step-by-step assembly process under hydrothermal conditions, a series of luminescent materials can be obtained by combining the diverse lacunary POT starting materials, various organic aromatic ligands, transition-metal (TM) and lanthanide (Ln) ions by the synergies of the moieties or intercomponent energy transfer. These compounds were characterized by elemental analyses, IR spectra, steady-state fluorescence spectra, thermogravimetric (TG) analyses, X-ray single-crystal diffraction, and so on. Furthermore, it is noted that we will apply the femtosecond time-resolved spectroscopy (transient absorption technique and pumping-excitation-fluorescence method) to study these physical processes in 3d-4f heterometallic polyoxotunstate-based fluorescent materials at the atomic and molecular levels, including the effects of excited states, energy transfer as well as charge transfer processes, and so on. In a word, all these not only provide us basic services to exploit and develop polyoxotungstate-based fluorescent materials, but also accumulate experience for the structural design and controllable synthesis of functional materials.

荧光材料在生物成像、太阳能利用、生物检测、半导体光学材料、药物代谢等领域都表现出巨大的应用前景。随着金属-氧簇化学迅猛发展，近年来合成过渡和稀土金属同时取代并在荧光方面有卓越性能的新型钨氧簇合物以及对这些新型荧光体系中详尽发光机理等核心问题的研究，是一个很有意义并富有挑战的课题。本申请项目主要是围绕3d-4f异金属构筑的钨-氧簇基荧光材料的设计合成、性能表征以及稳态-瞬态发光机理方面展开工作，重点是采用常温溶液法、一步或多步水热等方法通过稀土金属离子、缺位钨-氧簇前驱体、过渡金属离子以及有机小分子“协同作用”，制备性能优良的发光材料，并结合稳态荧光光谱与飞秒时间分辨瞬态吸收光谱技术，从原子、分子层次上研究钨-氧簇基荧光材料的发光机理，包括其中电子激发态性质、能量转移过程及光诱导电荷转移等过程的影响，进而为多酸基发光材料的开发研制以及功能材料的结构设计与可控合成提供重要的理论知识和参考意义。

随着科技的迅猛发展，3d-4f异金属修饰的钨-氧簇化学由于其丰富的结构类型以及在磁性、光学、电化学、电催化和材料科学领域的潜在应用，是目前无机化学领域发展迅猛的领域之一。其中，合成过渡和稀土金属同时取代并在荧光方面有卓越性能的新型钨氧簇合物以及对这些新型荧光体系中详尽发光机理等核心问题的研究，是一个很有意义并富有挑战的课题。本项目主要是围绕3d-4f异金属构筑的钨-氧簇基材料的设计合成、性能表征以及稳态-瞬态发光机理研究方面展开工作，重点是采用一步或多步水热合成等方法通过稀土金属离子、缺位钨-氧簇前驱体、过渡金属离子以及有机小分子“协同作用”，制备一系列性能优良的簇基材料，研究其性能及应用，并结合稳态荧光光谱与飞秒时间分辨瞬态吸收光谱技术，从原子、分子层次上研究钨-氧簇基荧光材料的发光机理，包括其中电子激发态性质、能量转移过程及光诱导电荷转移等过程的影响，对钨-氧簇基功能材料的开发研制以及结构设计与可控合成有重要的意义。