Vibrational and magnetic properties of [C2H5NH3][FeIIIMII(HCOO)6] (M=Mn, Ni) and [C2H5NH3][CrIIIMnII(HCOO)6] framework compounds

•[C2H5NH3][MIIIMII(HCOO)6] MIII=Fe, Cr; MII=Mn, Ni were grown.•X-ray diffraction indicates niccolite-type structure for the obtained compounds.•Raman and IR spectra are presented and assignment of modes is proposed.•IR and Raman spectra give evidence for weak amine-cavity interactions. We report syn...

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Bibliographic Details
Published in:Vibrational spectroscopy 2017-05, Vol.90, p.74-80
Main Authors: Mączka, M., Gągor, A., Pikul, A., Trzebiatowska, M.
Format: Article
Language:English
Subjects:
Cations
Diffraction
Ferromagnetism
Formate
High temperature
Holes
Infrared
Infrared radiation
Lattice vibration
Magnetic properties
Manganese
Metal compounds
Metal-organic framework
Nickel
Perovskite
Raman
Symmetry
Synthesis
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Summary:•[C2H5NH3][MIIIMII(HCOO)6] MIII=Fe, Cr; MII=Mn, Ni were grown.•X-ray diffraction indicates niccolite-type structure for the obtained compounds.•Raman and IR spectra are presented and assignment of modes is proposed.•IR and Raman spectra give evidence for weak amine-cavity interactions. We report synthesis, X-ray diffraction, magnetic and vibrational studies of three novel heterometallic MOFs, [C2H5NH3][FeIIIMII(HCOO)6] with M=Ni (EtFeNi) and Mn (EtFeMn) as well as [C2H5NH3][CrIIIMnII(HCOO)6] (EtCrMn) crystallizing in the niccolite type architecture (space group P3¯1c) with disordered ethylammonium (EtA+) cations located in the large cavities. Magnetic studies show that EtFeNi and EtFeMn exhibit ferromagnetic order below 43 and 38K, respectively, whereas EtCrMn remains paramagnetic at least down to 2K. Analysis of the Raman and IR data allowed us to propose assignment of the observed bands to the respective internal and lattice modes. These data give also evidence for weaker amine-cavity interactions compared to the perovskite analogues and show that this difference has significant effect on structure of the EtA+ cation. We also report that synthesis of Mg-analogues resulted in formation of ethylammonium magnesium formate with partially substituted Mg2+ (by Cr3+ or Fe3+) and EtA+ cations (by HCOOH molecules). These mixed-metal compounds have most likely the same R3¯symmetry as the high-temperature phase of undoped perovskite-type [C2H5NH3][Mg(HCOO)3].
ISSN:0924-2031
1873-3697
DOI:10.1016/j.vibspec.2017.04.004