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Partially Reversible Thermal-Induced Oxidation During a Dehydration Process in an H-bonded Supramolecular System.
The thermal behaviour of an H-bonded molecular network A based on [FeII (CN)6 ]4- anions and organic bisamidium cations 12+ was investigated. Heating was found to induce the partial oxidation of [FeII (CN)6 ]4- into [FeIII (CN)6 ]3- , together with a thermochromic effect and also a loss of crystallinity was evidenced from mid and far FT-IR spectroscopic data, XRPD and DSC/TGA analysis. Rehydration also partially reversed the redox reaction and its colour, and after that, a mixture of A with an amorphous phases was observed. FT-IR spectroscopy revealed that the oxidation of Fe(II) was accompanied by a deprotonation of the cation.
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