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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 inmethanolic solutions. Irradiation of the complexes intointraligand and/or ligand-to-metal charge-transfer bands induces aseries of photophysical and photochemical deactivation processesleading to Fe(II) and CH2O as final products in a 2:1 molar ratio. Formation of polystyrene containing bonded NCSgroup when irradiating the complexes in the presence of styrenemonomer used as a radical scavenger indicates that the primaryphotoreduction of Fe(III) to Fe(II) is accompaniedby the oxidation of NCS− ligand to •NCS radical. 4-R-benacen-ligands behave as an innocent moietyvirtually not participating in the photoinduced redox processes.The quantum yield of Fe(II) formation ΦFe(II) decreases significantly with increased wavelength of the incidentradiation, and is slightly influenced by the peripheral groups Rof the 4-R-benacen-ligands

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