Asymmetry and magnetism in bis(oximato)-bridged heterobimetallic compounds: a computational approach

A density functional study of exchange coupling was carried out for a series of heterobinuclear oximato-bridged transition metal complexes. Model calculations were used to examine the influence of the electronic configuration of the metal atoms on the coupling constants. This analysis was complemented by a study of the variation of the coupling constant with the most usual structural distortions within this family of compounds. The influence of the nature of the terminal ligands as well as that of the symmetry on the bridge were also investigated.     

About the calculation of exchange coupling constants in polynuclear transition metal complexes

The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data.     

Mössbauer studies on one-dimensional iron phthalocyanines

Summary Magnetic moments and⁵⁷Fe Mössbauer spectra at room temperature and at liquid nitrogen temperature of polynuclear ligand-bridged iron phthalocyanines, FePcL (L = pyrazine and 4,4-bipyridyl), are reported. The experimental data are in agreement with a pseudo-octahedral environment around the iron(II) cation. Partially oxidized derivatives, FePc(pz)I_0.26 and FePc(bipy)I_1.06 have been synthesized and their⁵⁷Fe Mössbauer spectra and magnetic moments within the same temperature range obtained. Oxidation is shown to be metal centred and the iodine is found to be in I^– form for FePc(pz)_0.26 and as both I^– and I ₃ ^– species for FePc(bipy)I_1.06. While the magnetic moment of FePc(pz) increases upon oxidation, the opposite occurs for FePc(bipy).     

Compositional changes in lime-based mortars exposed to different environments

Specimens of aerial and hydraulic lime-based mortars to be used in restoration works were prepared, hardened and subjected to different environments to study their compositional changes during setting, hardening and exposure to environment. Outside exposure, weathering cycles in a climatic chamber, SO₂-rich environment and indoor exposure (as control group) were selected to expose the mortars. XRD, FT-IR and TG-DTA analyses were performed at 7, 14, 21 and 28 days to determine the chemical and mineralogical composition, as well as the formation of the degradation products. Outside and SO₂-chamber exposures and increasing the relative humidity allowed faster carbonation (enhancing CO_2(g) dissolution) and hydration of hydraulic compounds. In SO₂-chamber, sulfate attack appears as a surface phenomenon, giving: gypsum in aerial specimens and gypsum and syngenite in hydraulic specimens.     

Synthesis and characterization of new di- and tri-nuclear cyano-bridged bis(dioximato)cobalt(III) complexes

Summary Several new neutral and cationic di- and tri-nuclear cyano-bridged bis(dioximato)cobalt(III) complexes have been synthesized and characterized (dioximato = dimethylglyoximato or diphenylglyoximato). These compounds are obtained through substitution of labile axial ligands by the nitrogen of the cyano-group in [Co(dioximato)₂(CN)₂]^– or [LCo(dioximato)₂(CN)] (L = H₂O, NH₃, or py). In the first case, the existence of only one band in the CN-stretching region of the i.r. spectrum at 2190–2200 cm^–1 is indicative of a trinuclear compound, while the presence of a second band at 2140 cm^–1 attributable to a terminal cyano-group indicates a dinuclear structure. In the presence of water, aquation of axial positions may take place at the same time as bridge formation, whereas the use of a non-aqueous solvent allows the preparation of complexes with pyridine or NH₃.