Comparative studies of vibrational properties and phase transitions in metal-organic frameworks of [NH4][M(HCOO)3] with M=Mg, Zn, Ni, Fe, Mn

•[NH4][M(HCOO)3] M=Ni, Fe, Mn were grown.•Raman and IR studies of [NH4][M(HCOO)3] were performed.•IR data confirmed an order–disorder character of the phase transitions.•Correlations between size and/or mass of divalent cation and wavenumbers were found.•Splitting and the activation energy for reori...

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Bibliographic Details
Published in:Vibrational spectroscopy 2015-03, Vol.77, p.17-24
Main Authors: Mączka, M., Szymborska-Małek, K., Ciupa, A., Hanuza, J.
Format: Article
Language:English
Subjects:
Bands
Infrared
Iron
Magnesium
Manganese
Metal-organic frameworks
MOF
Nickel
Phase transformations
Phase transitions
Raman
Zinc
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Summary:•[NH4][M(HCOO)3] M=Ni, Fe, Mn were grown.•Raman and IR studies of [NH4][M(HCOO)3] were performed.•IR data confirmed an order–disorder character of the phase transitions.•Correlations between size and/or mass of divalent cation and wavenumbers were found.•Splitting and the activation energy for reorientational motions of NH4+ is proportional to Tc. Room temperature experimental infrared (IR) and Raman spectra of [NH4][M(HCOO)3] compounds with M=Mg, Zn, Ni, Fe, Mn were analyzed in order to propose the assignment of the experimental bands to the respective internal and lattice modes. We also report temperature-dependent IR studies of [NH4][Ni(HCOO)3] and [NH4][Fe(HCOO)3] in the temperature range 5–295K, and compare them with the previously reported data for the Zn and Mg analogs. The temperature-dependent data provide deeper insight into mechanism of the phase transition and relationship between the phase transition temperature and chemical composition of the studied compounds.
ISSN:0924-2031
1873-3697
DOI:10.1016/j.vibspec.2015.02.003