Bio-inspired, side-on attachment of a ruthenium photosensitizer to an iron hydrogenase active site model
Bio-inspired, side-on attachment of a ruthenium photosensitizer to an iron hydrogenase active site model
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DOI：
10.1039/b606659c
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发表时间：
2006-01-01
影响因子：
4
通讯作者：
Ott, Sascha
中科院分区：
文献类型：
--
作者：
Ekstoem, Jesper;Abrahamsson, Maria;Ott, Sascha
描述了第一种钌 - 二铁配合物[(μ - pdt)Fe₂(CO)₅{PPh₂(C₆H₄CCbpy)}Ru(bpy)₂]²⁺ 1（pdt = 丙二硫醇盐，bpy = 2,2'-联吡啶），其中光活性的三（联吡啶）钌单元通过直接连接到一个铁中心的配体与铁氢化酶活性位点的模型相连。电化学和光物理研究表明，标题配合物的光诱导金属到配体电荷转移（MLCT）激发态定域在潜在的二铁受体单元上。然而，炔基联吡啶还原所需的相对较温和的电位以及容易被氧化的二铁部分导致激发态发生还原猝灭。这个过程产生一个瞬时氧化的二铁单元，这可以解释配合物1令人惊讶的高光敏感性。
The first ruthenium - diiron complex [(mu- pdt) Fe-2(CO)(5){PPh2(C(6)H(4)CCbpy)} Ru(bpy)(2)](2+) 1 (pdt = propyldithiolate, bpy = 2,2'-bipyridine) is described in which the photoactive ruthenium trisbipyridyl unit is linked to a model of the iron hydrogenase active site by a ligand directly attached to one of the iron centers. Electrochemical and photophysical studies show that the light-induced MLCT excited state of the title complex is localized towards the potential diiron acceptor unit. However, the relatively mild potential required for the reduction of the acetylenic bipyridine together with the easily oxidized diiron portion leads to a reductive quenching of the excited state, instead. This process results in a transiently oxidized diiron unit which may explain the surprisingly high light sensitivity of complex 1.