Molecular, spectroscopic, and magnetic properties of cobalt(II) complexes with heteroaromatic N(O)-donor ligands

Abstract

New [Co(SCN)2(L)4/2] complexes, where L = b-pic (1), pyCH2OH (2), py(CH2)3OH (3), 1,2,4- triazolo[1,5-a]pyrimidine (4), [CoCl2(urotrop)2] (5), and [Co(DMIM)3]Cl2 H2O (6) where urotrop = hexamethylenetetramine and DMIM = 2,20-bis(4,5-dimethylimidazolyl) were synthesized in simple reactions of CoCl2 6H2O with ammonia thiocyanate and pyridine type ligands or urotropine and diimidazolyl ligands with cobalt(II) chloride in methanol solutions. The orthorhombic crystallization for (1), (2), and (4), the monoclinic one for (3) and (5) as well as the hexagonal one for (6) were found. The plots of the overlap population density-of-states indicated nonbonding character of the interactions between pyridine derivatives ligands and cobalt(II) ions in the complexes (1)–(4). The electronic spectra showed almost perfect octahedral complex in the case of (6). The magnetic susceptibility measurements revealed paramagnetic behavior with low values of the Curie–Weiss temperature, positive for complex (5) and negative for the other ones, although the transition to collective magnetic state at low temperatures for (4) and (5) was evidenced by an observation of antiferromagnetic coupling with Ne´el temperature of 4.5 K and the ferromagnetic one with Curie temperature of 10 K, respectively.