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Synthesis and Electron‐Transfer Processes in a New Family of Ligands for Coupled Ru−Mn 2 Complexes
Author(s) -
Karlsson Erik A.,
Lee BaoLin,
Liao RongZhen,
Åkermark Torbjörn,
Kärkäs Markus D.,
Becerril Valeria Saavedra,
Siegbahn Per E. M.,
Zou Xiaodong,
Abrahamsson Maria,
Åkermark Björn
Publication year - 2014
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201402006
Subject(s) - excited state , electron transfer , photochemistry , chemistry , acceptor , electron acceptor , ligand (biochemistry) , catalysis , bipyridine , ruthenium , photoinduced electron transfer , redox , water splitting , crystallography , photocatalysis , inorganic chemistry , atomic physics , organic chemistry , crystal structure , physics , biochemistry , receptor , condensed matter physics
A series of [Ru(bpy) 3 ] 2+ ‐type (bpy=2,2′‐bipyridine) photosensitisers have been coupled to a ligand for Mn, which is expected to give a dinuclear complex that is active as a water oxidation catalyst. Unexpectedly, photophysical studies showed that the assemblies had very short lived excited states and that the decay patterns were complex and strongly dependent on pH. One dyad was prepared that was capable of catalysing chemical water oxidation by using [Ru(bpy) 3 ] 3+ as an oxidant. However, photochemical water oxidation in the presence of an external electron acceptor failed, presumably because the short excited‐state lifetime precluded initial electron transfer to the added acceptor. The photophysical behaviour could be explained by the presence of an intricate excited‐state manifold, as also suggested by time‐dependent DFT calculations.

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