稀土锗氧簇有机骨架的可控合成及对重金属离子荧光传感性能的研究

Fluorescent sensing technique has unique advantages in detecting heavy metal ions, and the key factor for it is the synthesis of fluorescent sensing materials. Lanthanide organic frameworks are important fluorescent sensing materials, but their design and controllable synthesis are restricted by the high coordination numbers and flexible coordination models of lanthanide ions, which further affect the acquisition of target sensing materials. In order to solve this problem, this project is proposed to use {Ln8Ge12} lanthanide germanate clusters as second building units and apply aromatic dicarboxylic acids to replace the coordinated H2O molecules in {Ln8Ge12}, accomplishing the controllable synthesis of lanthanide germanate cluster organic frameworks with superior properties. The fixed coordination H2O molecules in {Ln8Ge12} realize the predictability and controllability of material structures, while the rigidity, coplanarity and the bicephalous coordination model of aromatic dicarboxylic acids not only improve the stability and fluorescent property of materials, but also enhance the adjustability of porous structures and the mass transfer performance of heavy metal ions. Furthermore, this project will design and synthesize a series of lanthanide germanate cluster organic frameworks, and summarize their synthesis rules and structure characteristics. Then, their fluorescent property, sensing of heavy metal ions property and mechanisms will be explored in detail. Based on these, the structure-activity relationships will be summarized. In a word, all these not only provide us basic services to exploit and develop materials with strong fluorescence, but also accumulate information support for the structural design and controllable synthesis of target sensing materials.

荧光传感技术检测水中重金属离子有独特的优势，该技术的关键是荧光传感材料的制备。稀土有机骨架是一种重要的荧光传感材料，但由于稀土离子配位数高且配位模式多样，限制了其设计与可控合成，进而影响目标传感材料的获取。基于解决该问题，本项目拟以{Ln8Ge12}稀土锗氧簇为次级构筑单元，用二元芳香羧酸取代{Ln8Ge12}中的配位水分子，实现性能优异的稀土锗氧簇有机骨架的可控合成。{Ln8Ge12}中配位水分子的位置固定，实现了材料结构的可预测性与可控性，而二元芳香羧酸的刚性、共平面性及两端配位模式，提高了材料稳定性和荧光性能的同时，增强了孔结构的可调控性和重金属离子的传质。进一步，本项目拟设计合成一系列新型稀土锗氧簇有机骨架，总结其合成规律与结构特点，探究其荧光性能、对重金属离子的荧光传感性能与机理，总结其构效关系，为强荧光材料的开发研制和目标传感材料的设计与可控合成提供理论知识和参考意义。

荧光传感技术检测水中重金属离子有独特的优势，该技术的关键是荧光传感材料的制备。稀土有机骨架是一种重要的荧光传感材料，但由于稀土离子配位数高且配位模式多样，限制了其设计与可控合成，进而影响目标传感材料的获取。基于解决该问题，本项目以{Ln8Ge12}稀土锗氧簇为次级构筑单元，用芳香羧酸取代{Ln8Ge12}中的配位水分子，实现了性能优异的稀土锗氧簇有机骨架的可控合成。{Ln8Ge12}中配位水分子的位置固定，实现了材料结构的可预测性与可控性，而芳香羧酸的刚性和共平面性，提高了材料稳定性，增强了其荧光性能。进一步，本项目设计合成了一系列新型稀土锗氧簇有机骨架，总结了其合成规律与结构特点，探究了其荧光性能、对重金属离.子的荧光传感性能与机理，总结了其构效关系，为强荧光材料的开发研制和目标传感材料的设计与可控合成提供理论知识和参考意义。