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Visible light photolysis of dimanganese(III) µ-oxo bis-porphyrins, [Mn III (Por)] 2 O, was studied in three porphyrin systems with different electronic structures. Direct conversion of manganese (III) µ-oxo dimers to manganese(IV)-oxo porphyrins plus manganese(III) products has been observed in benzene solution upon light irradiation. The spectral signature of Mn IV (Por)(O) was further confirmed by production of the same species in the known experiment of the Mn III (Por)Cl with PhI(OAc) 2. Continuous irradiation of dimanganese(III) µ-oxo bisporphyrins in the presence of pyridine or triphenylphosphine gave rise to the formation of Mn II (Por)(Py) or Mn II (Por)(PPh 3) which were stable to be detected. A photo-disproportionation mechanism similar to that for diiron(III) µ-oxo bis-porphyrins was proposed to explain above photochemical behaviors of the three dimanganese(III) µ-oxo bis-porphyrins.

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