In this paper we report the temperature and pH dependent syntheses and systematic characterization of four new CoII/CoIII and NiII complexes with a pentadentate Schiff base ligand H3L obtained by condensing 1,3,-diaminopropan-2-ol with 2-hydroxyacetophenone in 1:2 molar ratio. The room temperature syntheses involving CoII and NiII nitrates and the ligand H3L lead to the isolation of the dinuclear species [Co2L2(H2O)] (1), and the mononuclear complex [Ni(LH)] (3), respectively, whereas refluxing at basic pH leads to the tetranuclear complexes, [CoII2Co III2L2(µ3-OMe) 2(NO3)(H2O)2]NO3· 2(H2O) (2), and [Ni4L2(µ3-OMe) 2(H2O)2]·2H2O (4). 1 is found to be a simple mono alkoxo-bridged CoIII dinuclear species, whereas 2 and 4 are both rhomb-like tetrameric complexes with double oxo bridges and µ3-methoxo bridges, derived from the methanol solvent, in an open dicubane arrangement. Moreover 2 shows six coordinate ordered CoII and CoIII ions and 4 has both six- and five-coordinate Ni II centers. Compound 3 is assigned a tentative mononuclear structure based on IR, UV-Vis spectroscopic, 1H-NMR and ESI mass study results and is supposed to have one NiII center coordinated with a ligand fragment in square planar geometry. The variable temperature magnetic susceptibility study for 2 and 4 is performed which indicate for both 2 and 4 the presence of intracluster dominant ferromagnetic interactions. © 2011 The Royal Society of Chemistry.