Valence-tautomeric RbMnFe Prussian blue analogues: composition and time stability investigation

Lionel Salmon, Esther J.M. Vertelman, Carlos B. Murgui, Saioa Cobo, Gábor Molnár, Petra Van Koningsbruggen, Azzedine Bousseksou

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Three different stoichiometric forms of RbMn[Fe(CN) ]y·zHO [x = 0.96, y = 0.98, z = 0.75 (1); x = 0.94, y = 0.88, z = 2.17 (2); x = 0.61, y = 0.86, z = 2.71 (3)] Prussian blue analogues were synthesized and investigated by magnetic, calorimetric, Raman spectroscopic, X-ray diffraction, and Fe Mössbauer spectroscopic methods. Compounds 1 and 2 show a hysteresis loop between the high-temperature (HT) Fe(S = 1/2)-CN-Mn(S = 5/2) and the low-temperature (LT) Fe(S = 0)-CN-Mn(S = 2) forms of 61 and 135 K width centered at 273 and 215 K, respectively, whereas the third compound remains in the HT phase down to 5 K. The splitting of the quadrupolar doublets in the Fe Mössbauer spectra reveal the electron-transfer-active centers. Refinement of the X-ray powder diffraction profiles shows that electron-transfer-active materials have the majority of the Rb ions on only one of the two possible interstitial sites, whereas nonelectron-transfer-active materials have the Rb ions equally distributed. Moreover, the stability of the compounds with time and following heat treatment is also discussed.
Original languageEnglish
Pages (from-to)760-768
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number6
Early online date14 Jan 2009
Publication statusPublished - Feb 2009


  • rubidium
  • charge transfer
  • nonstoichiometric compounds
  • manganese
  • iron


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