Temperature and solvent structure dependence of VO2+ complexes of pyridine-N-oxide derivatives and their interaction with human serum transferrin

The behaviour of the systems formed by VO(2+), 2-hydroxypyridine-N-oxide (Hhpo) and 2-mercaptopyridine-N-oxide (Hmpo) was studied both in solution and in the solid state through the combined application of spectroscopic (EPR and UV-Vis spectroscopy) and DFT methods. The geometry of solid bis-chelated complexes [VOL(2)], with L = hpo and mpo, is square pyramidal, but it can change to cis-[VOL(2)S], where S is a solvent molecule, when these are dissolved in a coordinating solvent. The equilibrium between the square pyramidal and cis-octahedral forms is strongly affected by solvent and temperature. At room temperature, the predominant species is [VOL(2)], which gives a pink colour to the solutions; at lower temperatures, the equilibrium is shifted--partially or completely--toward the formation of cis-[VOL(2)S], which is green. In an acidic environment and in the presence of an excess of ligand, [VOL(2)] can transform into the tris-chelated complex [VL(3)](+), in which vanadium loses the oxido ligand and adopts a hexa-coordinated geometry intermediate between octahedral and trigonal prismatic. 1-Methylimidazole (1-MeIm), which represents a model for His-N coordination, forms mixed complexes with stoichiometry cis-[VOL(2)(1-MeIm)], occupying an equatorial position. In the ternary systems VO(2+)-Hhpo-hTf and VO(2+)-Hmpo-hTf at room temperature and pH 7.4, besides (VO)hTf and (VO)(2)hTf, the mixed species cis-VO(hpo)(2)(hTf) and VO(mpo)(hTf) are observed, with the equatorial binding of an accessible histidine residue. Finally, the contribution of the N-oxide group to (51)V A(z) and A(iso) hyperfine coupling constants, which can be important in the characterisation of similar species, is discussed.