The syntheses and characterizations are reported for six new homo-and heterovalent manganese clusters, utilizing pyridyl functionalized beta-diketones ligands. The reaction of the trinuclear complex [Mn3O(O2CPh)(6)(H2O)(Py)(2)] with 1,3-di(pyridine-2-yl) propane-1,3-dione (dppdH) in CH2Cl2 resulted in a mixed-valence (Mn3Mn6MnIV)-Mn-II-Mn-III decanuclear cluster of formula [Mn10O7(dppd)(3)(O2CPh)(11)]center dot 4CH(2)Cl(2) (1). The structure of the core of 1 is based upon a centred tricapped trigonal prism. Reacting Mn(BF4)(2)center dot xH(2)O with dppdH and triethylamine (NEt3) in CH2Cl2-MeOH gave a rare, homoleptic hexanuclear cluster of formula [Mn-6(II)(dppd)(8)][BF4](4) (2) which has a triangular based core. Reaction of Mn(Y)(2)center dot xH(2)O, Y = NO3- or BF4-, with dppdH or 1-phenyl-3-(2-pyridyl)propane-1,3-dione (pppdH) in the presence of triethanolamine (teaH(3)) and NEt3 gave a heptanuclear disc like manganese core of general formula [Mn-7(II)(X)(6)(tea)(OH)(3)][Y](2)center dot solv (3) X = pppd(-) or dppd(-) and Y = NO3- or BF4-. The addition of N-(2-pyridinyl) acetoacetamide (paaH) to Mn(Y)(2)center dot 4H(2)O Y = NO3- or ClO4- in MeOH gave a second divalent heptanuclear cluster with a disc -like core of general formula [Mn-7(paa)(6)(OMe)(6)][X](2)center dot solv (4) (X = NO3- or ClO4-), whilst the addition of paaH to a mixture of Mn(NO3)(2)center dot 4H(2)O, teaH(3) and NEt3 in CH2Cl2-MeOH resulted in the formation of a mixed-valence (Mn2Mn2III)-Mn-II tetranuclear butterfly complex of formula [Mn-4(paa)(4)(teaH)(2)][NO3](2)center dot 2MeOH center dot 2CH(2)Cl(2) (5).