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Chem Sci. 2015 Apr 16;6(4):2323-2327. doi: 10.1039/c5sc00024f. Epub 2015 Jan 26.

Successive light-induced two electron transfers in a Ru-Fe supramolecular assembly: from Ru-Fe(ii)-OH2 to Ru-Fe(iv)-oxo.

Author information

1
Institut de Chimie Moléculaire et des Matériaux d'Orsay , Université Paris Sud , CNRS , F-91405 Orsay , CEDEX , France . Email: ally.aukauloo@u-psud.fr ; Email: frederic.banse@u-psud.fr.
2
SB2SM , iBiTec-S , CEA , CNRS , UMR 8221 , F-91191 , Gif-sur-Yvette , France . Email: winfried.leibl@cea.fr.

Abstract

In the present work we describe the synthesis and study of a RuII-FeII chromophore-catalyst assembly designed to perform the light-induced activation of an iron bound water molecule and subsequent photo-driven oxidation of a substrate. Using a series of spectroscopic techniques, we demonstrate that excitation of the chromophore unit with 450 nm light, in the presence of a sacrificial electron acceptor, triggers a cascade of electron transfers leading to the formation of a high valent iron(iv)-oxo center from an iron(ii)-bound water molecule. The activity of this catalytic center is illustrated by the oxidation of triphenyl phosphine.

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