Na Yong, Pan Jingxi, Wang Mei, Sun Licheng
State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology, 116012 Dalian, China.
Inorg Chem. 2007 May 14;46(10):3813-5. doi: 10.1021/ic070234k. Epub 2007 Apr 7.
Visible light-driven intermolecular electron transfer was observed from a reduced species Ru(bpy)3+, photogenerated via a reductive quenching of the ruthenium photosensitizer by a diethyldithiocarbamate anion, to bioinspired [2Fe2S] model complexes of the iron-only hydrogenase active site. The results indicate that Ru(bpy)32+ can act as a photoactive functional model of the [4Fe4S] cluster, playing the role of an electron-transfer relay. The photogenerated FeIFe0 species, which is proposed to be a crucial intermediate for proton reduction catalyzed electrochemically by the [2Fe2S] complexes, gives promise in the light-driven dihydrogen evolution using diiron complexes as surrogates of noble platinum catalysts.
观察到可见光驱动的分子间电子转移，该转移从通过二乙基二硫代氨基甲酸根阴离子对钌光敏剂进行还原猝灭而光生的还原态物种Ru(bpy)₃⁺，转移至仅含铁的氢化酶活性位点的仿生[2Fe₂S]模型配合物。结果表明Ru(bpy)₃²⁺可作为[4Fe₄S]簇的光活性功能模型，起到电子转移中继的作用。光生的Fe¹Fe⁰物种被认为是[2Fe₂S]配合物电化学催化质子还原的关键中间体，这为使用二铁配合物作为贵金属铂催化剂的替代物进行光驱动析氢带来了希望。
