6641-03-8Relevant articles and documents
Magnetic and structural properties of dinuclear singly bridged-phenoxido metal(II) complexes
Massoud, Salah S.,Spell, Mark,Ledet, Catherine C.,Junk, Thomas,Herchel, Radovan,Fischer, Roland C.,Trvnek, Zdenk,Mautner, Franz A.
, p. 2110 - 2121 (2015/01/30)
The reaction of a methanolic solution containing the bi-compartmental phenolic ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenol (LCl-OH) with MCl2·nH2O in the presence of NH4PF6 or NaClO4 afforded the dinuclear bridged-phenoxido dichlorido-metal(ii) complexes [Co2(μ-LClO)(H2O)2Cl2][Co2(μ-LClO)(MeOH)2Cl2](PF6)2 (1), [Ni2(μ-LClO)(MeOH)2Cl2]PF6 (2), [Ni2(μ-LClO)(MeOH)(H2O)Cl2]ClO4·1.25H2O (3), [Cu2(μ-LClO)Cl2]PF6·1/2MeOH (4) and [Zn2(μ-LClO)Cl2]PF6·MeOH (5). The complexes were characterized by elemental microanalyses, conductivity measurements, IR and UV-Vis spectroscopy, mass spectrometry and single crystal X-ray crystallography. Each M(ii) center within the dinuclear complex cations is octahedrally coordinated in complexes 1-3, and five-coordinated distorted square pyramidal in 4 and 5. Magnetic susceptibility measurements at variable temperature of the complexes 1-4 revealed weak to moderate antiferromagnetic coupling with |J| values = 8.38, 39.0, 30.2 and 0.79 cm-1, respectively. The results of DFT calculations correlate well with the experimentally determined antiferromagnetic coupling and show that the magnetic exchange coupling occurs mainly through the phenoxido bridge M-O-M. Implications of geometry around the central metal ion, M...M distance, M-O-M bond angle and overlapping of magnetic orbitals on the magnetic exchange coupling are discussed.