Oxidative polymerization of bromoiron(III) meso-tetrakis(3-thienyl)porphyrin gave a novel polymeric porphyrin complex randomly crosslinked at the 2,5-positions of the peripheral thienyl groups. The electrical semiconductivity of ca. 10-5 S/cm after I2 doping indicated that the polymer had a π-conjugated structure with a moderate delocalization of π electrons over the thienylporphyrin units. PM3 calculations for free-base models revealed that HOCO (the highest occupied crystal orbital) band width was reduced by introduction of the porphyrin moieties into the thienylene backbone and yet low HOCO-LUCO (the lowest unoccupied crystal orbital) gap was maintained, which accounted for the relatively low electrical conductivity of the porphyrin polymer. The modified electrode prepared by electropolymerization was redox-active due to the presence of iron(II/III) couple and the semiconductivity of the film, which served as a novel non-enzymatic electrochemical sensor for superoxide anion radical based on the facile electrocatalytic oxidation of the superoxide.
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