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Transition-metal phosphonate complexes have received a lot of attention in recent years primarily because of their potential applications in material chemistry.1-4 Three new Mn(Ⅲ)complexes with unusual topologies [MMn12ⅢCl(μ3-O)6(H2O)(PhPO3)9(PhPO3H)6(MeOH)6]·(solvent)x [M = K(1),Rb(2),Cs(3)] have been prepared by treatment of MnCl2·4H2O and NBu4nMnO4 with phenylphosphonic acid in the presence of different alkali metal hydrochloride.