新型光功能微孔稀土金属配位聚合物定向合成的量热学研究

Luminescent rare earth complexes exhibit excellent properties due to their high fluorescence intensity, narrow linewidth and long lifetime in luminescent materials and devices, chemical sensors, fluorescent probes and so on. However, directional synthesis of them is the bottleneck of its development. In this project, a series of microporous rare earth metal coordination polymers based on carboxylic acid ligands with strong absorption chromophore groups and nitrogen containing ligands were directionally synthetised by hydrothermal/solvothermal method. We regulated three line states of the photosensitive groups by modifying ligand substituent and introducing transition metal and non luminescent rare earth metal ions (La3+, Gd3+, Lu3+). By modifying the micropore structure of the auxiliary ligand and the modification of the pre modification, the fluorescence quenching can be inhibited, and the luminescent efficiency can be enhanced, and the stability of the complex can be improved. An accurate determination of the structure and luminescent properties of the target were performed by microcalorimetric technique. Thermodynamics of the directionally synthesize process of the target will be investigated by microcalorimetry in order to build the relationship of the reaction condition-structure-thermodynamics, and reveal their formation mechanism. Finally, the relation of ligand-micropore structure-luminescence property can be associated, which can reveal the influence of the type of conjugate aromatic carboxylic acid on the directional synthesis, structural changes and luminescence enhancement of the materials. This can provide the scientific basis to the development of the application of rare earth complex in all areas of optoelectronic information materials.

稀土发光配合物由于发光强度高、线宽窄、寿命长在发光材料与器件、化学传感器、荧光探针等方面均表现出优异的性能，然而其定向合成却成为深入发展的瓶颈。本项目拟利用含强吸收发色基团羧酸配体和含氮配体为有机构筑单元，采用水热/溶剂热方法，进行系列新型光功能微孔稀土配位聚合物的定向合成：通过配体取代基修饰、引入过渡金属和不发光稀土金属离子协同调节感光基团的三线态调控稀土离子发光；通过改变辅助配体和后修饰预先合成手段调控其微孔结构来抑制荧光淬灭、提高发光效率、增强配合物的稳定性；进行目标物的结构和发光性能的准确测定；通过微量热技术研究目标物定向合成过程的热动力学，关联反应条件-结构-热动力学信息，揭示其形成机理；最终关联配体-微孔结构-发光性能，揭示共轭配体类型等因素对材料定向合成、结构变化、发光性能增强的影响规律，为更好地开发稀土配合物在光电信息功能材料领域的应用研究提供科学依据。

稀土光功能金属配位聚合物由于发光强度高、线宽窄、寿命长在发光材料与器件、化学传感器、荧光探针等方面均表现出优异的性能而受到广泛关注。本项目利用水热合成法制备了两个系列的十个微孔稀土金属配位聚合物；利用后修饰预先合成手段对两种过渡金属配位聚合物进行稀土掺杂设计合成两个稀土复合物。通过多种测试技术对所得系列稀土微孔配位聚合物进行了精确的组成和结构分析，获得了其晶体结构、光谱性质、热稳定性、发光性质等基本物化性质。选取荧光性能优良的配聚物设计为荧光探针研究其在水溶液中对重金属离子、有机小分子、硝基爆炸物、抗生素和农药等环境污染物的荧光传感性能，探讨能量传递途径和发光机理。并采用微量热法研究了稀土配位聚合物的原位合成反应，获得了相应的热力学数据，为水热或溶液合成提供了理论支撑，从而得到了此类材料的定向合成的热力学信息，由此揭示合成过程中稀土微孔配位聚合物的形成机理，为此类配位聚合物的定向合成奠定基础。本项目的研究有望对更好地开发稀土配合物在光功能材料领域的应用研究提供科学依据,具有重要的科学意义。