Abstract
The heptanuclear and tetracationic nickel(II) complex [Ni7(μ3-OH)6(μ3-H2L)4](NO3)4·2MeOH (3·2MeOH); (H3L is 2,6-bis-[(3-hydroxy-propylimino)-methyl]-4-methyl-phenol), featuring four defective cubanes around a pivotal nickel(II) ion, has been obtained via hydroxido-bridge-induced assemblage of two Ni3 fragments. Presence of azido (N3−) and bromido (Br−) ions in reactions on the contrary lead to one ligand imine arm hydrolysis and formations of [Ni2(N3)2(μ-HL1)2(OH2)2] (1) and [Ni2Br2(μ-HL1)2(OH2)2] (2); where H2L1 is 2-hydroxy-3-[(3-hydroxy-propylimino)-methyl]-5-methyl-benzaldehyde. X-ray structural analyses of 3 show six symmetrically positioned NiII around a central NiII and bridged by six in situ generated hydroxido groups from solvent water molecules. Density functional theory (DFT) calculations have also been performed to predict magnetic behavior of the complexes. The spin density surface of compounds 1 and 2 has been also obtained.
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