title: Efficient [FeFe] hydrogenase mimic dyads covalently linking to iridium photosensitizer for photocatalytic hydrogen evolution.
abstract: Two [FeFe] hydrogenase mimics, [Fe(2)(μ-pdt)(CO)(5)L1] (L1 = PPh(2)SPhNH(2)) (Ph = phenyl) (2) and [Fe(2)(μ-pdt)(CO)(5)L2] (L2 = PPh(2)PhNH(2)) (3), and two molecular photocatalysts, [(CO)(5)(μ-pdt)Fe(2)PPh(2)SPhNHCO(bpy)(ppy)(2)Ir]PF(6) (bpy = bipyridine, ppy = 2-phenylpyridine) (2a) and [(CO)(5)(μ-pdt)Fe(2)PPh(2)PhNHCO(bpy)(ppy)(2)Ir](PF(6)) (3a), have been designed and synthesized, anchoring Ir(ppy)(2)(mbpy)PF(6) (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 CH(3)CN-H(2)O 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.
authors.affiliation: Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, China.
authors.forename: Hong-hua
authors.initials: HH
authors.lastname: Cui
authors.forename: Ming-qiang
authors.initials: MQ
authors.lastname: Hu
authors.forename: Hui-min
authors.initials: HM
authors.lastname: Wen
authors.forename: Guo-liang
authors.initials: GL
authors.lastname: Chai
authors.forename: Cheng-bing
authors.initials: CB
authors.lastname: Ma
authors.forename: Hui
authors.initials: H
authors.lastname: Chen
authors.forename: Chang-neng
authors.initials: CN
authors.lastname: Chen
mesh_terms: D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007495:Iridium / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D055668:Photochemical Processes; D017319:Photosensitizing Agents / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D007506:Iron-Sulfur Proteins; D009942:Organometallic Compounds; D017319:Photosensitizing Agents; D007495:Iridium; D006859:Hydrogen; C118830:iron hydrogenase; D006864:Hydrogenase