Details

Autor(en) / Beteiligte

• Barsan, Mirela M.
• Butler, Ian S.
• Fitzpatrick, Jessica
• Gilson, Denis F. R.

Titel

High-pressure studies of the micro-Raman spectra of iron cyanide complexes: Prussian blue (Fe4[Fe(CN)6]3), potassium ferricyanide (K3[Fe(CN)6]), and sodium nitroprusside (Na2[Fe(CN)5(NO)]·2H2O)

Ist Teil von

• Journal of Raman spectroscopy, 2011-09, Vol.42 (9), p.1820-1824

Ort / Verlag

Chichester, UK: John Wiley & Sons, Ltd

Erscheinungsjahr

2011

Quelle

Wiley Online Library - AutoHoldings Journals

Beschreibungen/Notizen

• The pressure dependences of the peaks observed in the micro‐Raman spectra of Prussian blue (Fe4[Fe(CN)6]3), potassium ferricyanide (K3[Fe(CN)6]), and sodium nitroprusside (Na2[Fe(CN)5(NO)]·2H2O) have been measured up to 5.0 GPa. The vibrational modes of Prussian blue appearing at 201 and 365 cm−1 show negative dν/dP values and Grüneisen parameters and are assigned to the transverse bending modes of the FeCNFe 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. The pressure dependences of the Raman features of Prussian blue, potassium ferricyanide, and sodium nitroprusside have been measured up to 5.0 GPa. The negative dν/dP values observed for the low wavenumber modes in Prussian blue may indicate negative thermal expansion properties. A pressure‐induced phase transition was observed for potassium ferricyanide. Strong interactions occur between vibrations of the NCFeNO group of atoms.