We report here the full description of a comprehensive synthetic methodology to isolate MnIIIMnIII, MnIIIMnIV, and MnIVMnIV dimers. The dimers [Mn2III/III(mu-O)(-OAc)2(MeL*)2][ClO4]2.CH2Cl2 (1), [Mn2III/IV(mu-O)2(mu-OAc)(MeL*)2][ClO4]2 (2) and [Mn2IV/IV(mu-O)2(mu-OAc)(MeL*)2][ClO4]3.2H2O (3) have been isolated, and complex 1 and 2 have been structurally characterized. Complex 3 has been used as an oxidant of a range of substituted phenolic substrates.