• Fischer, Roland C.
• Spell, Mark
• Massoud, Salah S.
• Junk, Thomas
• Ledet, Catherine C.
• Mautner, Franz A.
• Travnicek, Zdenek
• Herchel, Radovan

Abstract

The reaction of a methanolic soln. contg. 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]PF6·0.5MeOH (4) and [Zn2(μ-LClO)Cl2]PF6·MeOH (5).The complexes were characterized by elemental microanalyses, cond. measurements, IR and UV-visible spectroscopy, mass spectrometry and single crystal x-ray crystallog.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 temp. 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, resp.The results of DFT calcns. correlate well with the exptl. detd. 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. [on SciFinder(R)]

Topics

• impedance spectroscopy
• single crystal
• mass spectrometry
• density functional theory
• susceptibility
• spectrometry