Abstract
Iron(III) complexes of the formcis-[Fe(SB(X - K)] in whichSB2− are open-chain tetradentateSchiff base N2O2-ligands ofacacen,benacen orsalen type, andX - K− are bidentate anions of kojic acid (5-hydroxy-2-hydroxymethyl-4H-pyran-4-one) or other γ-pyranones undergo photoredox transformations when being irradiated in methanol into intraligand orLMCT bands. The quantum yields of the photoredox reactions depend on the peripheral constitution of the N2O2 ligands, the substituentsA andB of the ligandsX - K−, and the wavelength of irradiation λirr. The proposed mechanism involves the population of photoredox reactiveLMCT states by photophysical deactivation steps, primary photoredox formation ofX - K radicals and Fe(II), and subsequent “dark” redox processes giving back the anionsX - K− and the final products Fe(II) and formaldehyde formed in the molar ratio 2:1.
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