Efficient [FeFe] hydrogenase mimic dyads covalently linking to iridium photosensitizer for photocatalytic hydrogen evolution
Efficient [FeFe] hydrogenase mimic dyads covalently linking to iridium photosensitizer for photocatalytic hydrogen evolution
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高效[FeFe]氢化酶模拟二元体与铱光敏剂共价连接，用于光催化析氢
DOI：
10.1039/c2dt31618h
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发表时间：
2012-01-01
影响因子：
4
通讯作者：
Chen, Chang-neng
中科院分区：
文献类型：
--
作者：
Cui, Hong-hua;Hu, Ming-qiang;Chen, Chang-neng
两个[FeFe]氢酶模拟物[Fe-2(MU-PDT)(CO)(5)L1](L1=PPh2SPhNH2)(Ph=苯基)(2)和[Fe-2(MU-PDT)(CO)(5)L2](L2=PPh2PhNH2)(3)和两个分子光催化剂[(CO)(5)(MU-PDT)-Fe2PPh2SPhNHCO(BPY)(Ppy)(2)Ir]PF6(BPY=联吡啶，设计合成了PPy=2-苯基吡啶)(2a)和[(CO)(5)(MU-PDT)-Fe2PPh2PhNHCO(Bpy)(Ppy)(2)Ir](Pf6)(3a)，通过形成酰胺键将Ir(Ppy)(2)(MBpy)pF6(mBPy=4-甲基-4‘-甲酰基-2，2’-联吡啶)(PS)锚定在配合物2和3的铁中心上。以三乙胺(TEA)为电子供体，在CH3CN-H2O溶液中，利用可见光(>；400 nm)，成功地构建了分子二元组2a、3a和分子间体系2、3与PS的光诱导产氢反应。H-2产生的时间依赖关系和光谱研究表明，在膦配体上添加一个S原子可以调节H-2的放氢活性。在超分子体系中，以2a为光催化剂得到的最高析氢周转数(吨)为127，在多组分体系中，以催化剂2为基础得到的最高析氢周转数为138。密度泛函理论计算表明，第二配位球上的S原子使配合物2比配合物3更容易接受电子，从而提高了光诱导制氢的活性。
Two [FeFe] hydrogenase mimics, [Fe-2(mu-pdt)(CO)(5)L1] (L1 = PPh2SPhNH2) (Ph = phenyl) (2) and [Fe-2(mu-pdt)(CO)(5)L2] (L2 = PPh2PhNH2) (3), and two molecular photocatalysts, [(CO)(5)(mu-pdt)-Fe2PPh2SPhNHCO( bpy)(ppy)(2)Ir]PF6 (bpy = bipyridine, ppy = 2-phenylpyridine) (2a) and [(CO)(5)(mu-pdt)-Fe2PPh2PhNHCO( bpy)(ppy)(2)Ir](PF6) (3a), have been designed and synthesized, anchoring Ir(ppy)(2)(mbpy) PF6 (mbpy = 4-methyl-4'-carbonyl-2,2'-bipyridine) (PS) to one of the iron centers of complexes 2 and 3 by forming amide bonds. Molecular dyads 2a, 3a and the intermolecular systems 2, 3 with PS have also been successfully constructed for photoinduced H-2 production using triethylamine (TEA) as a sacrificial electron donor by visible light (>400 nm) in CH3CN-H2O solution. The time-dependence of H-2 generation and spectroscopic studies suggest that the activity of H-2 evolution can be tuned by addition of a S atom to the phosphane ligand. The highest turnover numbers (TON) of hydrogen evolution obtained are 127, using 2a as a photocatalyst in a supramolecular system, and 138, based on catalyst 2 in a multi-component system. Density functional theory (DFT) computational studies demonstrate that the S atom in the second coordination sphere makes complex 2 accept an electron more easily than 3 and improves the activity in light-induced hydrogen production.