Abstract
In CoFe Prussian Blue Analogs (PBAs), a small difference in the number of alkali cation per unit cell can lead to drastic differences in the properties of the PBA. We investigate the origin of this effect in order to be able to control it and design new functional materials for data storage devices. Here we characterize the Cs0.7Co4[Fe(CN)6]2.8.17 H2O and Cs2Co4[Fe(CN)6]3.3.11H2O PBAs by Co K-edge in situ XAS. For both PBAs, the photo-induced (PI) CoIIIFeII→CoIIFeIII charge transfer and the different involved states (room temperature, ground and PI) are described. In the case of the Cs0.7 PBA, the relaxation from the CoIIFeIII PI state towards the CoIIIFeII ground state is monitored and quantified. All the results, fully consistent with previous magnetometry and Co L3-edge XAS studies, are discussed with respect to the electronic structure of the Co ions in the different involved states.
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