二茂铁功能化的金属有机大环模拟氢化酶光催化硝基还原

Ferrocene-Functionalized Metal-Organic Macrocycles Mimicking Hydrogenase for Photocatalytic Nitro Reduction

使用二茂铁构筑了2个新型金属有机大环:M_(Cu)和M_(Fe)。2个大环化合物有效猝灭了有机染料的荧光,并可触发光致电子转移。较低的还原电位导致M_(Cu)在光催化质子还原和硝基还原2个反应中表现出更好的催化性能。底物的大尺寸导致硝基还原过程的效率降低。用Michaelis‑Menten机理对光催化体系进行了验证,揭示了底物与催化剂之间相互作用的重要性。

Two novel metal‑organic macrocycles(M_(Fe) and M_(Cu)) were constructed using the flexible and redox‑active ferrocene ligand.The macrocycles effectively quenched the fluorescence of organic dyes and exhibited the capability to trigger the photoinduced electron transfer.Due to relatively lower reduction potentials,M_(Cu) exhibited better catalytic features for proton reduction and could better catalyze the reduction of nitro compounds.The large size of the substrates leads to a decreased efficiency in the nitro reduction process.The Michaelis‑Menten mechanism was used to verify the photocatalytic system,which revealed the importance of the interaction between substrate and catalyst.