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Issue 40, 2011
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Manganese-Schiff base complexes as catalysts for water photolysis

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Abstract

Four manganese(III)-Schiff base complexes (1–4) of formula [MnLn(H2O)2]2(ClO4)2·mH2O (n = 1–4; m = 0, 1) have been prepared. The multidentate H2Ln Schiff base ligands consist of 3R,5R-substituted N,N′-bis(salicylidene)-1,2-diimino-2,2-dimethylethane, where R = OEt, OMe, Br or Cl. The complexes have been thoroughly characterized by elemental analysis, mass spectrometry, magnetic susceptibility measurements, IR, UV, paramagnetic 1H NMR and EPR spectroscopies. Other properties, including redox studies and molar conductivity measurements, have also been assessed. The crystal structure of 1 was solved by X-ray diffraction, which revealed the dimeric nature of the compound through μ-aqua bridges. The ability of these complexes to split water has been studied by water photolysis experiments, with the oxygen evolution measured in aqueous media in the presence of a hydrogen acceptor (p-benzoquinone), the reduction of which was followed by UV-spectroscopy. The discussion of the photolytic behaviour includes advances in the knowledge of the structural motifs and the chemical activity of this type of complex, as revealed by the development of several characterization techniques in the last decade. Parallel-mode MnIII EPR shows that complexes 1–4 not only mimic reactivity but also share some structural characteristics from partially assembled natural OEC clusters.

Graphical abstract: Manganese-Schiff base complexes as catalysts for water photolysis

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Supplementary files

Article information


Submitted
12 Apr 2011
Accepted
25 Aug 2011
First published
15 Sep 2011

Phys. Chem. Chem. Phys., 2011,13, 18069-18077
Article type
Paper

Manganese-Schiff base complexes as catalysts for water photolysis

G. González-Riopedre, M. I. Fernández-García, A. M. González-Noya, M. Á. Vázquez-Fernández, M. R. Bermejo and M. Maneiro, Phys. Chem. Chem. Phys., 2011, 13, 18069
DOI: 10.1039/C1CP21154D

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