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

Šima, Jozef; Izakovič, Mário; Žitňanský, Marián

doi:https://doi.org/10.1155/IJP/2006/78234

International Journal of Photoenergy

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Volume 2006 | Article ID 078234 | https://doi.org/10.1155/IJP/2006/78234

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

Jozef Šima,¹Mário Izakovič,¹and Marián Žitňanský¹

Received10 Nov 2004

Revised27 Jun 2005

Accepted15 Jul 2005

Published12 Feb 2006

Abstract

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.

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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.

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