氧化还原活性金属-有机框架材料的合成及性能研究

Coordination-driven metal-organic frameworks (MOFs) are a very attractive and interesting class of multifunctional materials due to their extensive applications in gas storage and separations, energy storage, nonlinear optics, electronic devices, catalysis, and drug delivery and other fields. This research project will focus on design and synthesis of functional organic ligands containing the Tetrathiafulvalene (TTF) core. A series of redox metal-organic frameworks with functionalized interior cavity surface based on these ligands and metal ions will be synthesized. The magnetic, solid-state electrochemical, conductivity, the adsorption and separation properties of these complexes will be investigated according to the structure of these MOFs. Furthermore, the electronic state of the framework can be modulating via oxidative doping. The properties such as the magnetic behavior, conductivity and the gas absorption were also modified by I2 doping. In addition, the mechanism, influence factors and the relationship between the structure and conductivity will be studied, which will provide an alternative approach for the design and preparation of multifunctional framework materials.

配位作用驱动的金属－有机框架(MOFs)化合物在气体吸附与分离、能量存储、非线性光学、电子器件、催化和药物传输等方面存在着广泛的应用，是目前多功能材料研究的热点之一。本研究计划将设计、合成具有良好性质的含四硫富瓦烯基元的有机配体，并通过控制有机配体的尺寸和结构及与金属离子配位能力，定向制备新型的具有特定孔穴或内部微环境的氧化还原活性MOFs。根据所获得的金属-有机框架化合物的结构特征，对框架的磁性、电化学、导电、气体吸附等性质进行研究。并通过掺碘将框架氧化成自由基，进而实现对磁性、导电以及气体吸附等性能的调控。深入探讨机理与影响因素，研究结构与性能的构-效关系，为设计、合成多功能金属-有机框架材料提供新的方法和途径。

金属－有机框架(MOFs)化合物在气体吸附与分离、能量存储、非线性光学、电子器件、催化和药物传输等方面存在着广泛的应用。本项目主要聚焦于氧化还原活性的框架材料。借助于分子晶体学工程相关技术，构建多功能框架材料。首先利用功能导向的策略，合成了多种电化学活性的含四硫富瓦烯或镍二硫烯基元的有机配体。利用水热方法或者溶液扩散方法定向制备新型氧化还原活性MOFs。此外利用多价态金属构筑了氧化还原活性的框架材料。除了表征了金属-有机框架化合物的结构外，对框架材料的磁性、电化学、导电、传感、发光等性质进行了研究。研究了阴离子的模板效应、溶剂交换、碘氧化掺杂等对框架材料结构及性能的调控。探讨了结构与性能的构-效关系，为新型多功能金属-有机框架材料的研究增添了新鲜内容，并提供了可靠的实验和理论依据。