Structure and chromotropism properties of an unsymmetrical alkoxo-bridged nickel(II) cubane-like complex

Abstract

A new tetranuclear cubane-like complex, [Ni4(L)4Cl4(H2O)3(EtOH)]·(H2O), has been synthesized from the reaction of a metal salt with the bidentate ligand 2-hydroxymethylpyridine (LH), and its crystal structure, spectroscopic and chromotropic properties have been studied. The complex has a [Ni4O4] core comprising a distorted cubane arrangement, of which four nickel(II) ions were bridged by μ3-alkoxo moieties. Each nickel(II) was coordinated to three μ3-alkoxo oxygens, one pyridine nitrogen and one chloride. The peripheral ligation was completed by an oxygen atom of water or ethanol ligand, which participated in intramolecular hydrogen bonding. Chromotropism properties of the complex including solvato-, thermo-, and ionochromism were investigated. The complex displayed strong ionochromism and shows high-sensitive and selective activity toward CN− and SCN− anions in the presence of other halides and pseudo-halides. The solvatochromic property of the complex was analyzed by a multi-parametric equation using SPSS/PC software. The stepwise multiple linear regression method demonstrated that the acceptor power of the solvent plays the most important role in the observed negative solvatochromism of the compound. It shows reversible thermochromism in solution due to loss of the weakly coordinated water and ethanol from the nickel(II) units.