基于平面型二核席夫碱配合物基元的发光d-f杂金属MOFs的组装

The metal-organic frameworks (MOFs) as a new type of hybrid materials have many advantages such as diverse structures, flexible syntheses, high specific area and easy functionalization, showing distinctive physical and chemical properties in the luminescence, electricity, magnetism, catalysis, adsorption and separation etc. As a new type of functional material, the interesting luminescent property of MOFs provides a unique research platform for the design and development of the luminescent materials in the solid state. Based on planar binuclear metal Schiff base complexes as second building block units(SBU), which contains two terminal pyridine/imidazole groups with strong intramolecular electron transfer and good luminescent properties, via assembly of different binuclear units or reacting with silver salt and trimesic acid/pyromellitic acid as well as their aromatic derivatives, a series of new fluorescent heterometallic MOFs are constructed.This project focuses on studying the sensitization of planar transition-metal units on Ln(III) luminescence and exploring the relationship between their structures and luminescence properties. Considering microporous nature of the resulting 3-D MOFs, effect of the exchange and adsorption behaviors on the responsed/induced luminescence properties from different guest molecules will be also investigated. This project aims at effective designing and synthesizing the new solid luminescent MOFs from the structure and function of materials, and revealing their luminescent mechanism and further providing some experimental and theoretical bases for the development and utilization of new luminescent materials.

金属有机框架配合物（MOFs）作为一类新型的杂化材料，具有结构多样、合成灵活、高比表面积和易功能化等特点，在光、电、磁、催化等方面展现出独特的物理与化学性质。作为一类新型多功能材料，其有趣多样的发光性能使其为固体发光材料的设计开发提供了独特的研究平台。本项目基于强的分子内电子转移特性与发光性能良好的平面型双吡啶/吡唑端基的二核席夫碱配合物为组装基元，通过稀土/过渡金属双核单元的相互组装或与银盐及对称芳香族多羧酸类桥联配体反应,构筑新型发光杂金属MOFs配合物。研究过渡金属单元对稀土发光的敏化作用，探究MOFs结构与发光性能间的关系。合理利用三维MOFs微孔孔道，研究产物对不同客体分子交换、吸附能力，探究材料的客体响应/诱导发光性能。本项目旨在从结构和功能的角度有效设计合成新型金属有机框架类固体发光材料，揭示该类材料的发光机理，为新型发光材料的开发利用提供一定的实验和理论积累。

金属有机框架配合物（MOFs）作为一类新型的杂化材料，具有结构多样、合成灵活、高比表面积和易功能化等特点，在光、电、磁、催化等方面展现出独特的物理与化学性质。本项目基于强的分子内电子转移特性与发光性能良好的平面型双吡啶/吡唑端基的二核席夫碱配合物为组装基元，通过稀土/过渡金属双核单元的相互组装及与对称芳香族多羧酸类桥联配体反应，构筑了系列新型发光杂金属MOFs配合物。研究了过渡金属单元对稀土发光的敏化作用，探究MOFs结构与发光性能间的构效关系。合理地利用了三维MOFs微孔孔道，系统地研究了产物对不同客体分子交换、吸附能力的影响，探究了主体框架材料的客体（如金属离子、硝基芳香化合物等）响应/诱导发光性能，总结了构效关系。. 此外,在探究MOFs的对客体的荧光响应的同时，本项目还发现MOFs基材料可.(1)高效吸附二氧化碳或乙炔，能够有效分离CO2/CH4、CO2/N2、C2H2/C2H4，在工业上有较好的应用前景。(2)直接或为前驱体煅烧制得的各种材料如氮掺杂碳材料、金属氧化物等, 通过变化反应温度、起始反应物投料比、掺杂物种类与量等因素得到不同结构与形貌的微纳米材料作为锂/锂硫电池电极/隔膜材料都表现出较好的性能。