稀土微孔配位聚合物的可控合成及客体响应的微量热学

The rare earth porous coordination polymers exhibit excellent properties in storing gas, catalyzing the organic reactions, ions exchanging, luminescence and magnetism and so on. However, the controllable synthesize of these materials is the bottleneck of its development. This project intends to prepare series of rare earth porous coordination polymers using rare earth/rare earth-oxygen clusters as the inorganic building units, combining the rigid/soft multi-dentate aroma carboxyl ligands and the long-chain multi-pyridine ligands as the organic building units, with hydrothermal/ solvothermal and solution synthesize methods. The as-prepared porous materials would be compositionally and structurally characterized by EA, IR, UV, MS, NMR, XPS, BET, single crystal X-ray diffraction techniques, which will provide the exact structural information. By in-situ microcalorimetric technique, thermodynamics of the synthesize process of rare earth porous coordination polymers will be investigated in order to discover their formation mechanism and build the structure-activity relationship of the reaction condition-structure-thermodynamics, and provide the theoretic supports for the controllable synthesize of the material. The adsorption properties and the guest exchanging experiments will be measured and studied by microcalorimetric method to build their thermodynamics model and select the best adsorption and desorption rare earth porous coordination polymers. This investigation will offer the new idea and theoretic direction for the controllable synthesize of rare earth porous coordination polymers.

稀土微孔配位聚合物在气体储存、有机反应催化、离子交换、发光、磁性等方面都表现出优异的性能，然而其可控合成却成为深入发展的瓶颈。本项目拟以稀土/稀土-氧簇为无机构筑单元，结合刚性/柔性的多齿芳香羧酸及长链多吡啶配体为有机构筑单元，采用水热/溶剂热合成法和溶液合成法，制备系列稀土微孔配位聚合物材料。通过EA、IR、UV、MS、NMR、XPS、BET、单晶X-射线衍射等技术对其进行组成和结构分析表征，获得其准确的结构信息；通过原位量热技术开展系列稀土微孔配位聚合物的合成过程的热动力学研究，揭示其形成机理，建立其反应条件-结构-热动力学信息的构效关系，为此类材料的可控合成提供理论依据和支撑；通过微量热技术进行吸脱附及客体交换过程的热量变化，确定其对客体的响应情况，建立过程热动力学模型，优选出吸脱附效果最佳的稀土微孔配合物材料。本项目的研究将为稀土微孔配位聚合物材料的可控合成提供崭新的思路和理论指导

【摘要】 稀土微孔配位聚合物的结构多样性和性能优异性促进了其在众多领域的广泛应用。本项目以稀土/稀土-氧簇无机构筑单元和多齿芳香羧酸有机构筑单元为基础，采用多种合成方法制备了六个系列稀土微孔配位聚合物。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、吸附性质、磁学性质、热稳定性、发光性质等基本物化性质。通过原位量热技术研究了六个系列的稀土微孔配位聚合物的合成过程的热动力学过程，主要研究了水热过程和溶液合成过程，获得了相关热力学数据，由此揭示合成过程中稀土微孔配聚物的形成机理，为此类配聚物的可控合成提供理论依据。根据稀土微孔配位聚合物对客体溶剂分子的荧光响应，结合微量热技术进行客体分子响应的能量变化，由此建立结构-荧光-能量相关性，优选对客体分子有响应的最佳稀土微孔配位聚合物。本项目的研究有望通过微量热法对稀土微孔配位聚合物材料的可控合成与客体分子的荧光响应提供理论依据和指导,具有重要的科学意义。