Mixed valence states in cobalt iron cyanide

Cobalt iron cyanide with both Co and Fe in mixed valence states were prepared and characterized. In this mixed valence system the cobalt atom is found both as high spin Co(2+) and low spin Co(III) while iron always appears in low spin state to form two solid solutions: Co(2+)Co(III) hexacyanoferrates (II,III), and Co(2+)Co(III) hexacyanoferrate (II). Such solid solutions have the following formula units: (Co2+)x(CoIII)1−xK[(FeII)1−x(FeIII)x(CN)6]·12H2O and (Co2+)1.5x(CoIII)1−xK[FeII(CN)6]·yH2O (0⩽x⩽10⩽x⩽1, 1⩽y⩽141⩽y⩽14). Compounds within these two series were characterized from Infrared, Mössbauer, X-ray diffraction and thermo-gravimetric data, and magnetic measurements at low temperature. A model for their crystal structure is proposed and the structure for a representative composition refined from XRD powder patterns using the Rietveld method. A simple and reproducible procedure to prepare these solid solutions is provided. Within hexacyanoferrates, such mixed valence states system in both metal centres shows unique features, which are discussed from the obtained data.