Co(II) Optical Absorption in Spinels: Infrared and Ligand-Field Spectroscopic Study of the Ionicity of the bond. Magnetic Structure and Co2+→Fe3+MMCT in Ferrites. Correlation with the Magneto-Optical Properties

The analysis of the infrared and ligand field spectra of COM2O4spinels reveals that the ionicity of these compounds varies in the following order aluminate > gallate > ferrite and chromite > rhodite and cobaltite. A linear relation has been established between the Δ(LO-TO)1splitting, Racah parameter and the ionic-covalent parameterSSp=ΣICP+tetra∑ICPocta. The influence of strong superexchange interactions on the optical spectrum of cobalt ferrites has been studied. The cation distribution has been established by EXAFS and XANES measurements. The cluster (CoFeO10)15–is characterized by a large MMCT transition Co2+→Fe3+at 1.65–1.7 eV (FWMH: 1.35–1.95 eV). The4A2→4T1(P) tetrahedral cobalt(II) in ferrimagnetic compounds is overlapped by the MMCT band. This study and the reinvestigation of the iron(III) electronic spectrum is ferrites may explain the magneto-optical properties of mixed cobalt-ferrites.

Copper(II) complexes with 1-phenyl-4,6-dimethylpyrimidine-2-thione. Chemical, spectroscopic, magnetic, conductivity and polarographic studies

New copper(II) complexes of general composition: CuLX2.nH2O (X = Cl-, n = 0.25; X = NO3-, n = 0.5), Cu2L3Cl4.2H2O, CuL2X2.H2O (X = ClO4-, BF4- and NO3-) and Cu2L7X4 (X = ClO4-, BF4- and NO3-), where L = 1-phenyl-4,6-dimethylpyrimidine-2-thione, have been isolated. Chemical and thermal analyses, conductivity, magnetic susceptibility, infrared and ligand field spectroscopic data and, for the perchlorate complexes also polarographic studies, are reported. Diagnostic IR bands frequencies of counter-ions, χ(Cu-X) modes and ligand field spectra for the mono-and bis-ligand compounds, having an equatorial [CuNSCl2], [CuNSO2] and [CuN2S2] microsymmetry, indicate a coordinating character of some anions, suggesting an elongated octahedral geometry for these complexes. For the [Cu2L7]X4 (X = ClO4-, BF4- and NO3-) complexes, which exhibit at room temperature subnormal magnetic moments, a polynuclear structure with the copper(II) in a roughly square-pyramidal environment, is proposed. Polarographic data for the perchlorate complexes and for the Cu(ClO4)2-L system at various ligand concentrations, have shown that in DMF solution the prevailing species are [CuL2]2+, [CuL3]2+ and [Cu2L7]4+ confirming the oxidation state II for the copper ions in the [Cu2L7]X4 complexes.