Synthesis, electrochemical and spectroelectrochemical characterization of iron(III) tetraarylporphyrins containing four β,β′-butano and β,β′-benzo fused rings

Abstract

Six iron(III) tetraarylporphyrins containing four [Formula: see text]-butano or [Formula: see text]-benzo fused rings were synthesized and characterized by electrochemistry and spectroelectrochemistry in nonaqueous media. The examined compounds are represented as butano(TpYPP)FeCl and benzo(TpYPP)FeCl, where TpYPP is a dianion of the meso-substituted porphyrin, Y is a CH[Formula: see text], H or Cl substituent on the para-position of the four meso-phenyl rings and butano and benzo are the [Formula: see text]-substituents on each of the four pyrrole rings of the compound. Up to three reductions are observed for each Fe(III) butano- and benzoporphyrin in CH[Formula: see text]Cl[Formula: see text] or pyridine containing 0.1 M TBAP, the first of which is assigned in each case to a metal-centered electron transfer. The second reduction is also metal-centered in CH[Formula: see text]Cl[Formula: see text] and leads to formation of an Fe(I) porphyrin, but it is porphyrin ring-centered and gives an Fe(II) porphyrin [Formula: see text]-anion radical reduction product when pyridine is used as the solvent. The effects of the solvent and type of fused ring system (butano or benzo) on the UV-vis spectra and electrochemical properties of the Fe(III) porphyrins are discussed and comparisons are made to both the structurally related non-[Formula: see text]-substituted iron porphyrins and earlier described butano- or benzotetraarylporphyrins containing Cu(II) or Co(II) central metal ions.