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International Journal of Photoenergy
Volume 2006, Article ID 78234, 5 pages

Mechanism of deactivation processes of excited iron(III) thiocyanato complexes with benacen-type ligands

Department of Inorganic Chemistry, Slovak Technical University, Radlinského 9, Bratislava 81237, Slovakia

Received 10 November 2004; Revised 27 June 2005; Accepted 15 July 2005

Copyright © 2006 Jozef Šima et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


The complexes [Fe(4-R-benacen)(CH3OH)(NCS)], where 4-R-benacen2 are tetradentate open-chain N,N-ethylenebis(4-R-benzoylacetoneiminato) N2O2-ligands (R=H, Cl, Br, OCH3), are redox stable in the dark in methanolic solutions. Irradiation of the complexes into intraligand and/or ligand-to-metal charge-transfer bands induces a series of photophysical and photochemical deactivation processes leading to Fe(II) and CH2O as final products in a 2:1 molar ratio. Formation of polystyrene containing bonded NCS group when irradiating the complexes in the presence of styrene monomer used as a radical scavenger indicates that the primary photoreduction of Fe(III) to Fe(II) is accompanied by the oxidation of NCS ligand to NCS radical. 4-R-benacen-ligands behave as an innocent moiety virtually not participating in the photoinduced redox processes. The quantum yield of Fe(II) formation ΦFe(II) decreases significantly with increased wavelength of the incident radiation, and is slightly influenced by the peripheral groups R of the 4-R-benacen-ligands.