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1 Polish Journal of Chemistry

1 1998

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Preparation and photoinduced processes of ferric complexes containing fluoride and tetradentate salen-type ligands

Sima J., Mrazova J., Kotocova A.

Polish Journal of Chemistry

1998

Vol. 72, nr 9

2079-2086

Tetradentate open-chain Schiff base ligands R-salen (R-salen are N,N'-ethylenebis(R-salicylideneiminato) dianions) and fluoride anions F(-) coordinate to the iron(III) central atom in methanol forming the complexes trans-[Fe(R-salen)(CH3OH)F]. The complexes are redox stable in the dark. Photoexcitation into their intraligand or ligand-to-metal charge transfer excited states leads to the photoreduction of Fe(III) to Fe(II), as a product of metanol oxidation the radical CH2OH was identified. The final products of the redox processes, Fe(II) and CH20, are formed in a 2:1 molar ratio. The efficiency of the photoredox processes is strongly wavelenght dependent and influenced by the peripheral groups R of the tetradentate ligands. A mechanism of deactivation processes is proposed and the influence of the peripheral groups R on the photoredox efficiency and electrochemical properties of the complexes is discussed.