Redox-Active Metal-Organic Frameworks: Novel Entatic State Catalysts?

氧化还原活性金属有机框架：新型熵状态催化剂？

• 批准号: 202904373
• 负责人: Professor Dr. Karsten Reuter
• 金额: --
• 依托单位: Lehrstuhl für Festkörperchemie
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2011
• 资助国家: 德国
• 起止时间: 2010-12-31 至 2015-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/202904373?language=en
• 关键词: Redox; Active; Metal; Organic; Frameworks

Porous, redox-active metal-organic frameworks (MOFs) shall be developed which are constructed from aromatic N-donor ligands (e.g. pyrazolate or triazolate moieties) and openshell 3d transition metal ions. Previous investigations have demonstrated that the use of heterocyclic aromatic N-donors leads to greatly enhanced hydrolytic stability of the MOF compounds, which is a necessary condition for catalytic oxidation processes. Particular attention will be addressed to the specific advantages of embedding a multinuclear transition metal cluster into a rigid 3D coordination framework (“entatic state catalyst”). Thus, the spectroscopic and catalytic properties of solid MOF catalysts shall be compared with special emphasis laid upon gas phase reactions. Quantum chemical investigations will address different oxidation states of the electronically coupled metal sites in multinuclear clusters, and their role in catalytic oxidation or oxygenation cycles. Density functional theory (DFT) based on general gradient approximation (GGA) and hybrid functionals is applied to investigate ground and excited state properties of the MOFs. Special attention will be paid to important properties like vibrational and UV/VIS spectroscopy as well as to the redox behaviour of the envisaged compounds.

应开发由芳族N-供体配体（例如吡唑或三唑部分）和开壳3d过渡金属离子构建的多孔氧化还原活性金属有机框架（MOF）。先前的研究已经证明，使用杂环芳族N-供体导致大大增强的MOF化合物的水解稳定性，这是催化氧化过程的必要条件。将特别注意到嵌入到一个刚性的3D协调框架（“Entatic态催化剂”）的多核过渡金属簇的具体优点。因此，固体MOF催化剂的光谱和催化性能应与特别强调的气相反应进行比较。量子化学研究将解决多核簇中电子耦合金属位点的不同氧化态及其在催化氧化或氧化循环中的作用。基于广义梯度近似和杂化泛函的密度泛函理论研究了MOFs的基态和激发态性质。特别注意将支付给重要的属性，如振动和UV/维斯光谱以及设想的化合物的氧化还原行为。