Two series of β,β′-pyrrole
butano- and benzo-substituted
mangenese(III) tetraarylporphyrins were synthesized and characterized
with regard to their spectral and electrochemical properties. The
investigated compounds have the general formula butano(Ar)4PorMnCl and benzo(Ar)4PorMnCl, where Por is the dianion
of the porphyrin and Ar is a p-CH3Ph,
Ph or p-ClPh group on each of the four meso-positions of the macrocycle. Each manganese(III) butano- or benzoporphyrin
was examined in CH2Cl2 and/or pyridine containing
0.1 M tetra-n-butylammonium perchlorate and the data
then were compared to that of the parent tetraarylporphyrins having
the same meso-substituents. Up to four reductions
are observed for each compound, the first being metal-centered to
generate a Mn(II) porphyrin, and the second and third being porphyrin
ring-centered to give a Mn(II) porphyrin π-anion radical and
dianion, respectively. The one-electron reduced manganese porphyrins
have an ESR spectrum with signals at g
⊥= 5.6–5.8 and g
// = 2.0, indicating
a mixture of the four- and five-coordinated Mn(II) complexes in a
high-spin state (3d5, S = 5/2, I = 5/2). Data from cyclic voltammetry and spectroelectrochemistry
both suggest that formation of the porphyrin dianion is followed by
a chemical reaction at the electrode surface to give an electroactive
phlorin anion. The effects of solvent and porphyrin substituents on
ultraviolet–visible light (UV-vis) spectra, redox potentials,
and electron transfer mechanisms are discussed.