Ekström Jesper, Abrahamsson Maria, Olson Carol, Bergquist Jonas, Kaynak Filiz B, Eriksson Lars, Sun Licheng, Becker Hans-Christian, Akermark Björn, Hammarström Leif, Ott Sascha
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 10691, Stockholm, Sweden.
Dalton Trans. 2006 Oct 14(38):4599-606. doi: 10.1039/b606659c. Epub 2006 Aug 8.
The first ruthenium-diiron complex [(mu-pdt)Fe2(CO)5{PPh2(C6H4CCbpy)}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.
首个钌 - 二铁配合物[(μ - pdt)Fe₂(CO)₅{PPh₂(C₆H₄CCbpy)}Ru(bpy)₂]²⁺ 1（pdt = 丙基二硫醇盐，bpy = 2,2'-联吡啶）被报道，其中光活性三(联吡啶)钌单元通过直接连接到其中一个铁中心的配体与铁氢化酶活性位点模型相连。电化学和光物理研究表明，标题配合物的光诱导MLCT激发态定位于潜在的二铁受体单元。然而，炔基联吡啶还原所需的相对温和的电位以及易于氧化的二铁部分反而导致激发态的还原猝灭。这个过程导致二铁单元瞬间被氧化，这可能解释了配合物1令人惊讶的高光敏性。
