The employment of 2-(beta-naphthalideneamino)-2-(hydroxymethyl)-1-propanol (LH3) in cobalt, nickel, and copper chemistry has led to the isolation of five new metallic complexes with interesting magnetic properties. More specifically, the reaction of Co(OAc)(2)center dot 4H(2)O with LH3 in MeOH in the presence of NEt3 under solvothermal conditions forms the complex [(Co2Co3II)-Co-III(L)(2)(LH)(2)(L')(OAc)]center dot 8.5MeOH (1 center dot 8.5MeOH; L' = monoanion of 2-hydroxy-1-naphthaldehyde), while in nickel chemistry, a similar reaction of Ni(OAc)(2)center dot 6H(2)O with LH3 in MeCN in the presence of NEt3 under high pressure/temperature forms the complex [Ni-II(LH2)(2)]center dot 2MeCN (2 center dot 2MeCN). Repeating the same reaction in MeOH and switching from Ni(OAc)(2)center dot 4H(2)O to NiSO4 center dot 4H(2)O produces the complex [Ni-4(II)(HL)(3)(OMe)-(MeOH)(3)](SO4)(0.5)center dot 2MeOH (3.2MeOH) under solvothermal conditions. Furthermore, in copper chemistry, the reaction of Cu-2(OAc)(4)center dot 2H(2)O with LH3 in the presence of NEt3 in MeOH under solvothermal conditions affords the complex [Cu-4(II)(LH)(4)] (4), while the same reaction under ambient temperature and pressure conditions forms [Cu-4(II)(LH)(4)]center dot 3.5MeOH center dot 2.25H(2)O (5 center dot 3.5MeOH center dot 2.25H(2)O). Complex 1 is a mixed-valent [(Co2Co3II)-Co-III] complex, consisting of three edge-sharing [Co-3] triangles. Complex 2 is a nickel(II) monomer in which the central metal is found in an octahedral geometry, while complex 3 describes a [Ni-4(II)] cubane. Complexes 4 and 5 may be considered as structural isomers because they possess the same formulas but different topologies: 4 describes a highly distorted [Cu-4(II)(OR)(4)](4+) eight-membered ring, while 5 consists of a distorted [Cu-4(II)(mu(3)-OR)(4)](4+) cubane. In addition, 5 can be converted to 4 in excellent yield under solvothermal conditions. Direct-current magnetic susceptibility studies have been carried out in the 5-300 K range for complexes 1 and 3-5, revealing the possibility of a high-spin ground state for 1, an S = 4 ground state for 2, and diamagnetic ground states for 4 and 5.