Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume -, Issue 11, Pages 1549-1555Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.200601023
Keywords
Prussian blue analogues; magnetic properties; phase transitions; Raman spectroscopy
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A series of Prussian blue analogues, RbxMn[Fe(CN)6]y center dot zH(2)O with different stoichiometries have been synthesized. Elemental analyses reveal a quasilinear decrease in x and y when z increases. Some of these samples present a first-order phase transition between the Mn-II-Fe-III and Mn-III-Fe-II electronic states with large thermal hysteresis loops observed in the magnetic susceptibility. The phase-transition temperatures correlate with the stoichiometry, but quantitative predictions cannot be made because of the disordered nature of the compounds. Contrary to previous literature reports, calorimetric and Raman spectroscopic measurements reveal that the charge-transfer phase transition is accompanied by a significant entropy change, Delta S = 48-59 JK(-1) mol(-1), of mainly vibrational origin. In addition to the thermal phase transition, Raman spectra also show that below ca. 120 K a photoinduced Mn-III-Fe-II to Mn-II-Fe-III. conversion occurs in certain stoichiometries. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007.
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