Bifunctional molecular metals based on BEDO-TTF radical cation salts with paramagnetic [MIII(CN)6]3− anions, M = Fe, Cr, (Fe0.5Co0.5)

The crystals of new bifunctional molecular metals based on bis(ethylenedioxy)tetrathiafulvalene (BEDO-TTF) radical cation salts with paramagnetic [M(CN)6]3− anions, where M = Fe, Cr, (Fe0.5Co0.5), and a diamagnetic [Co(CN)6]3− anion of general formula: β″-(BEDO-TTF)6Ax[M(CN)6]·G2−x, where G is a guest solvent molecule (acetonitrile or dimethylformamide); A = H3O+, K+; x ∼ 0.5, were synthesized by electrocrystallization. Conductivity measurements show metallic behavior for all these salts down to a temperature of 4.2 K. The effect of the BEDO-TTF intracrystalline field on the magnetic properties of the [Fe(CN)6]3− complex anion was observed. Random distribution of these complexes along BEDO-TTF layers modulates the local crystalline environment of these anions and splitting of their Zeeman sublevels. Powder-like EPR spectrum of [Fe(CN)6]3− anions in these crystals corresponds to this space disorder. The intracrystalline field of the BEDO-TTF layers strongly changes the temperature dependence of effective magnetic moment of the [Fe(CN)6]3− anion in comparison with the K3Fe(CN)6. This fact indicates redistribution of spin density inside complexes and changes in their effective spin value under the action of the BEDO-TTF environment.