Abstract
Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co+2FeII) and ferricyanides (Co+2FeIII) in an ozone flow. The CN stretching bands occur at 2085 cm−1 for Co+2FeII and at 2160 cm−1 for Co+2FeIII. After the ozonization process of Co+2FeII, an intense band approximately at 2125 cm−1 is detected. This intermediate band must correspond to a mixed valence state of the type: FeII−CN−Co2+−NC−FeIII Mossbauer spectra recorded “in situ” during the ozonization of Co+2FeII show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mossbauer and infrared spectra of the aged samples of the Co+2FeII after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.
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