Photocatalytic hydrogen evolution by [FeFe] hydrogenase mimics in homogeneous solution.
To mimic [FeFe] hydrogenases (H(2)ases) in nature, molecular photocatalysts 1 a, 1 b, and 1 c anchoring rhenium(I) complex S to one of the iron cores of [FeFe]-H(2)ases model complex C, have been constructed for H(2) generation by visible light in homogeneous solution. The time-dependence of H(2) evolution and a spectroscopic study demonstrate that the orientation of S and the specific bridge in 1 a, 1 b, and 1 c are important both for the electron-transfer step from the excited S* to the catalytic C, and the formation of unprecedented long-lived charge separation for 1 a (780 micros), 1 b, and 1 c (>2 ms) in [FeFe]-H(2)ases mimics. The fast forward electron-transfer step from the excited S* to the catalytic C but the slow back electron-transfer step of the charge-recombination in the designed photocatalysts 1 a, 1 b, and 1 c are reminiscent of the behavior of [FeFe]-H(2)ases in nature.
Wang
Wen-Guang
WG
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, PR China.
Wang
Feng
F
Wang
Hong-Yan
HY
Si
Gang
G
Tung
Chen-Ho
CH
Wu
Li-Zhu
LZ
D040761:Biomimetic Materials / Q000737:chemistry*; D002384:Catalysis; D004579:Electron Transport; D006859:Hydrogen / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism; D017319:Photosensitizing Agents / Q000737:chemistry
D007506:Iron-Sulfur Proteins; D017319:Photosensitizing Agents; D006859:Hydrogen; C118830:iron hydrogenase; D006864:Hydrogenase