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High‐pressure studies of the micro‐Raman spectra of iron cyanide complexes: Prussian blue (Fe 4 [Fe(CN) 6 ] 3 ), potassium ferricyanide (K 3 [Fe(CN) 6 ]), and sodium nitroprusside (Na 2 [Fe(CN) 5 (NO)]·2H 2 O)
Author(s) -
Barsan Mirela M.,
Butler Ian S.,
Fitzpatrick Jessica,
Gilson Denis F. R.
Publication year - 2011
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.2931
Subject(s) - prussian blue , potassium ferricyanide , chemistry , ferricyanide , raman spectroscopy , analytical chemistry (journal) , cyanide , ferrocyanide , spectral line , inorganic chemistry , nuclear magnetic resonance , electrode , electrochemistry , physics , optics , chromatography , astronomy
The pressure dependences of the peaks observed in the micro‐Raman spectra of Prussian blue (Fe 4 [Fe(CN) 6 ] 3 ), potassium ferricyanide (K 3 [Fe(CN) 6 ]), and sodium nitroprusside (Na 2 [Fe(CN) 5 (NO)]·2H 2 O) have been measured up to 5.0 GPa. The vibrational modes of Prussian blue appearing at 201 and 365 cm −1 show negative dν/d P values and Grüneisen parameters and are assigned to the transverse bending modes of the FeCNFe linkage which can contribute to a negative thermal expansion behavior. A phase transition occurring between 2.0 and 2.8 GPa in potassium ferricyanide is shown by changes in the spectral region 150–700 cm −1 . In the spectra of the nitroprusside ion, there are strong interactions between the FeN stretching mode and the FeNO bending and the axial CN stretching modes. The pressure dependence of the NO stretching vibration is positive, 5.6 cm −1 GPa −1 , in contrast to the negative behavior in the iron(II)‐ meso ‐tetraphenyl porphyrinate complex. Copyright © 2011 John Wiley & Sons, Ltd.