Magnetic ordering of NiII4 Cubane complexes through hydrogen bonds

Abstract

Abstract The serendipity synthesis of the 2-hydroxy-3-methoxy-benzaldehyde or o-vanillin nickel(II) cubane complex, obtained by ourselves and other workers, can be rationalized to give the cubane in a high yield by direct use of 2-hydroxy-3-methoxy-benzaldehyde (H-ovan). The structural determinations of crystals obtained according to the two experimental processes show that the complex formulated [(MeOH)Ni(μ3-OMe)(ovan)]4 (ovan = deprotonated form of o-vanillin) is characterized in the two cases. Ni-Ni ferromagnetic interactions (JNiNi = 5.8 cm−1) giving an S = 4 ground state are active in the Ni4 cubane. Replacement of methanol molecules coordinated to the Ni ions by a diol, an amino-alcohol or an amino-ether allows self-association of these Ni4 units according to two different ways: by direct coordination bonds through the diol ligand or by hydrogen bonds involving the OMe groups of o-vanillin located at the periphery of the cubane and the hydrogen atoms of the primary amine functions. This association is suggested in the two cases by the presence of out-of-phase signals (χ”) when ac susceptibility measurements are performed at different frequencies. These molecules do not behave as SMM for these χ” signals, that are not frequency-dependent, correspond to the establishment of a three-dimensional ordering.