Structural, MALDI-TOF-MS, Magnetic and Spectroscopic Studies of New Dinuclear Copper(II), Cobalt(II) and Zinc(II) Complexes Containing a Biomimicking u-OH bridge

CRISTINA NUÑEZ; RUFINA BASTIDA; ALEJANDRO MACÍAS; LAURA VALENCIA; NICOLÁS I. NEUMAN; ALBERTO C. RIZZI; CARLOS D. BRONDINO; PABLO J. GONZÁLEZ; JOSÉ LUIS CAPELO; CARLOS LODEIRO

DALTON TRANSACTIONS

ROYAL SOC CHEMISTRY

Año: 2010 vol. 39 p. 11654 - 11663

1477-9226

The Py2N4S2 octadentate coordinating ligand afforded dinuclear cobalt, copper and zinc complexes and the corresponding mixed metal compounds. The overall geometry and bonding modes have been deduced on the basis of elemental analysis data, MALDI-TOF-MS, IR, UV-vis and EPR spectroscopies, single-crystal X-Ray diffraction, conductivity and magnetic susceptibility measurements. In the copper and zinc complexes, a μ-hydroxo bridge links the two metal ions. In both cases, the coordination geometry is distorted octahedral. Magnetic and EPR data reveal weakly antiferromagnetic high spin Co(II) ions, compatible with a dinuclear structure. The magnetic characterization of the dinuclear Cu(II) compound indicates a ferromagnetically coupled dimer with weak antiferromagnetic intermolecular interactions. The intra-dimer ferromagnetic behaviour was unexpected for a Cu(II) dimer with such μ-hydroxo bridging topology. We discuss the influence on the magnetic properties of non-covalent interactions between the bridging moiety and the lattice free water molecules.