The synthesis and electrochemical behaviour of water soluble manganese phthalocyanines: Anion radical versus Mn(I) species

The following MnPc derivatives were synthesized: 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5a), quaternized 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5b), 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (6a) and quaternized 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH)(6b). Spectro-electrochemistry shows that the reduction of Mn(II)Pc to Mn(I)Pc occurs only when the complexes are in their quaternized form (5b and 6b). The reduction (to Mn(I)Pc(−2)) of the quaternized form occurs at a lower potential than that (to Mn(II)Pc(−3)) of the unquaternized form. This observation suggests that metal reduction (to Mn(I)Pc(−2)) versus ligand reduction (to Mn(II)Pc(−3)) in Mn(II)Pc complexes depends on the nature of the ring substituents