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The photophysics and photochemistry of phthalocyanine complexes of magnesium (MgPc), aluminum chloride (ClAlPc) and zinc (ZnPc) are studied in N, N′-dimethylformamide (DMF). The values obtained for the photophysical and photochemical parameters are normal for simple metallophthalocyanine (MPc) complexes. Protonation of the azomethine bridges reduced the photoactivities of the complexes considerably; however the excited triplet states of the protonated species are more stable towards ground state oxygen. The interaction of the non-protonated MPcs with ground state oxygen is shown to be diffusion-assisted, with bimolecular rate constant values of the order of 10 10 M -1 .s -1 . MgPc could not be protonated; it was easily demetalated by the protonating acid. The kinetics of the demetalation yielded the rate equation: Rate = 0.1[MgPc][H + ] 2/3 .