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Cobalt hexacyanoferrates have a relatively low energy barrier for the charge transfer between cobalt and iron atoms. Thatenergy barrier can be overcome by irradiation with light in the ultraviolet-blue region or through the sample heating. Suchfeature for that charge transfer process is determined by structural and compositional factors. In this contribution the roleof a second metal partially substituting to Co in the material composition on the heat induced charge transfer is studied.Samples of the solid solution Co 3–x T x [Fe(CN) 6 ] 2 yH 2 O with T = Mn, Ni, Cu, Zn and Cd, were prepared by a simple synthetic route and their behavior on moderate heating, from 80to 160 °C, was evaluated. The behavior of the solid solution on heating was followed by infrared, X-ray diffraction and Mössbauerdata. The heat induced charge transfer appears to be favored once the crystal water is removed, when the metal-metal interaction,through the CN bridges, reaches its maximum strength. From this fact, when a metal like Cu, Zn and Cd, with a relatively weakinteraction with the coordinated water molecules and, as a consequence, with a low dehydration temperature, is present inthe material structure, a lower activation energy is required to be able the heat induced charge transfer. Even in the presenceof a second divalent transition metal occupying a fraction of the structural sites for Co, the charge transfer was observed,which is particularly pronounced in the 120–140 °C temperature range. The heat-induced charge transfer was also evaluatedfrom the photo-induced inverse process in the heated samples using photo-acoustic spectroscopy.

Heat Induced Charge Transfer in the Solid Solution Co 3–x T x [Fe(CN) 6 ] 2 yH 2 O with T = Mn, Ni, Cu, Zn and Cd