On the mechanism of the photoinduced reduction of an adduct of ferricytochrome C with a poly(4-vinylpyridine) polymer containing –ReI (CO)3(3,4,7,8-tetramethyl-1,10-phenanthroline) pendants

Changes in the UV–vis absorption spectrum revealed the formation of adducts between the ReI polymer and ferricytochrome C, FeIII-Cyt c. Different morphologies for the ReI polymer and the adducts formed between the ReI polymer and FeIII-Cyt c were observed by TEM. The reduction of the ReI chromophores in the polymer, achieved by the reductive quenching of the MLCT excited state of the ReI polymer by triethylamine (TEA) and/or by the reaction between e−solv and {[(vpy)2vpyReI(CO)3(tmphen)+]}n∼200 in pulse radiolysis experiments, produces –ReI(CO)3(tmphen) and –ReI(CO)3(tmphenH)+ as the main species. The reductive quenching of the MLCT of the ReI polymer by TEA was followed by a rapid electron transfer from the –ReI(CO)3(tmphen) to the FeIII center in the heme to produce ferrocytochrome C, FeII-Cyt c.