含共轭电子有机功能配体调控的多核稀土离子嵌入的杂多钨氧簇材料的合成、结构、发光性能及发光机理研究

Exploring polyoxometalate-based luminescent materials and improving their luminous performances are a challenging research subject. However, to date, relevant reports on organic-inorganic hybrid multi-nuclear rare-earth-encapsulated heteropolyoxotungstate cluster materials and their luminous performances are very rare. In this project, we plan to utilize the combination reaction strategy of the organic-water mixed solvent method (or organic solvent method ) and microwave heating method to prepare novel conjugated-electron containing functional organic ligand controlled multi-nuclear rare-earth-encapsulated heteropolyoxotungstate cluster materials and discover some key controlling factors in the reactions. The luminescent properties and luminescent dynamics of as-synthesized materials will be systematically investigated. Their luminous mechanisms will be mainly discussed and the corresponding physical models will be established. We will intensively explore the influences of the doping ratios of different rare earth ions on the luminous performances to search white-light emitting and upconversion target materials. Moreover, we will prepare the thin film materials of target materials by means of the spin-coating technology and probe their related luminescent properties. The systematic investigations on luminous performances and luminescent dynamics of conjugated-electron containing functional organic ligand controlled multi-nuclear rare-earth-encapsulated heteropolyoxotungstate cluster materials in this project will drive polyoxometalate-based materials into the field of rare earth luminescent materials and lay the research foundations for the potential applications in information display, energy-saving lighting and photoelectric detection, etc. Therefore, this study has important theory significance and potential practical application value.

探索以多金属氧簇为基质的发光材料并改善其发光性能是一项具有挑战性的研究课题。目前有关有机–无机杂化多核稀土离子嵌入多钨氧簇材料的报道及发光性能的研究很少。本项目采用有机溶剂–水混合溶剂（或有机溶剂）与微波加热相结合的方法来制备含共轭电子有机功能配体的多核稀土离子嵌入杂多钨氧簇材料，发现合成反应的关键控制因素。对目标材料的发光性能和发光动力学过程等进行系统研究，重点探究其发光机理，建立相应物理模型。探索不同稀土掺杂比例对发光性能的影响，发现具有白光和上转换发光的目标材料。借助旋涂技术制备目标薄膜材料，探索其相关的发光性质。本项目系统开展含共轭电子有机功能配体的多核稀土离子嵌入的杂多钨氧簇材料及薄膜材料的发光性能及发光机理研究，推动多金属氧簇材料向稀土发光材料领域迈进，为进一步开发其在信息显示、节能照明、光电探测等领域的应用奠定基础，具有重大理论研究意义和潜在现实应用价值。

本项目利用有机增溶剂和有机配体共同调控的策略，重点探索钨酸盐、稀土离子、杂原子组分和有机功能配体之间的反应匹配关系，成功实现了有机功能配体、稀土离子和杂多钨氧簇片段的控制组装，制备了27系列多核稀土嵌入的杂多钨氧簇材料，建立了一套制备有机功能配体调控的多核稀土嵌入的杂多钨氧簇材料的制备方法，总结出有机功能配体与稀土离子在杂多钨氧簇片段研究体系中的协同配位和结构调控的一些规律。对获得的目标材料的可见和近红外激发光谱、发射光谱、荧光寿命行为等进行了测试，考察了有机功能配体或杂多钨氧簇片段对稀土离子发光的敏化作用，探究了发光过程中有机功能配体、稀土离子和杂多钨氧簇片段之间的能量转移现象，阐明了一些光致发光过程中的物理机理和动力学过程的控制因素。尽管项目研究过程基本顺利，还存在一些不足之处，在以后的工作中进行深入探索和解决。本项目实施期间，在Nanoscale、J. Mater. Chem. C、Inorg. Chem.、Inorg. Chem. Front.、Dalton Trans.等期刊上发表SCI收录论文41篇，其中影响因子大于4.0的29篇，获批发明专利6项，荣获厅级科技奖励4项，培养硕士研究生10名，参与培养博士研究生3名，参加国内外学术会议27人次，邀请6名金属氧簇材料领域专家来我校进行交流。该项目的实施，不但推动有机–无机杂化多核稀土嵌入的杂多钨氧簇材料制备化学的发展，拓宽杂多钨氧簇化学的研究范畴，也将推动多金属氧簇材料向稀土发光材料领域逐步迈进，为多金属氧簇合成化学的持续发展和多金属氧簇材料的性能拓展提供新的发展动力，为进一步开发多金属氧簇材料在信息显示、节能照明、光电探测等领域的应用研究奠定基础。