First-order structural transition in the multiferroic perovskite-like formate [(CH3)2NH2][Mn(HCOO)3]

Andújar, Manuel; Gómez-Aguirre, L. Claudia; Pato-Doldan, Breogán; Yáñez-Vilar, S.; Artiaga, Ramón; Llamas-Saíz, Antonio L.; Manna, Rudra Sekhar; Schnelle, Frank; Lang, Michael; Ritter, Franz; Haghighirad, Amir A.; Señarı́s-Rodrı́guez, M. A.

doi:10.1039/c3ce42411a

Cited by 83 publications

(79 citation statements)

References 34 publications

(69 reference statements)

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“…This value is very large and even larger than the 46 K GPa −1 value expected for [(CH 3 ) 2 NH 2 ][Mn(HCOO) 3 ]. 30 As mentioned already in the Introduction, for AzMn analogue the transition into the monoclinic phase was also observed at very low pressure, that is, at 0.41−0.66 GPa. 22 Thus, our result confirms very high flexibility of the AzM frameworks and shows that the first pressure-induced phase transition is associated with the freezing of ing-puckering motions.…”

Section: ■ Results and Discussionmentioning

confidence: 78%

Raman and IR Studies of Pressure- and Temperature-Induced Phase Transitions in [(CH₂)₃NH₂][Zn(HCOO)₃]

et al. 2014

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Temperature- and pressure-dependent studies of Raman and IR spectra have been performed on azetidinium zinc formate, [(CH2)3NH2][Zn(HCOO)3]. Vibrational spectra showed distinct anomalies in mode frequencies and bandwidths near 250 and 300 K, which were attributed to structural phase transitions associated with the gradual freezing of ring-puckering motions of the azetidinium cation. Pressure-dependent studies revealed a pressure-induced transition near 0.4 GPa. Raman spectra indicate that the structure of the room-temperature intermediate phase observed near 0.4 GPa is the same as the monoclinic structure observed at ambient pressure below 250 K. The second phase transition was found near 2.4 GPa. This transition has strong first-order character and is associated with strong distortion of both the zinc formate framework and azetidinium cations. The last phase transition was found near 7.0 GPa. This transition leads to lowering of the symmetry and further distortion of the zinc formate framework, whereas the azetidinium cation structure is weakly affected.

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Section: ■ Results and Discussionmentioning

confidence: 78%

Raman and IR Studies of Pressure- and Temperature-Induced Phase Transitions in [(CH₂)₃NH₂][Zn(HCOO)₃]

et al. 2014

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“…NTE 3 ] showed usual contraction of all lattice parameters upon cooling both in the high and low temperature phases. 22 …”

Section: Structural Studiesmentioning

confidence: 97%

Synthesis and order–disorder transition in a novel metal formate framework of [(CH₃)₂NH₂]Na_0.5Fe_0.5(HCOO)₃]

et al. 2014

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We report the synthesis, crystal structure, thermal, dielectric, Raman, infrared, and magnetic properties of [(CH3)2NH2][Na(0.5)Fe(0.5)(HCOO)3] (DMNaFe), the first metal formate framework templated by organic cations, presenting an ABO3 perovskite architecture with NaO6 octahedra as building blocks of the framework. On the basis of Raman and IR data, assignment of the observed modes to respective vibrations of atoms is proposed. We have found that DMNaFe undergoes a structural phase transition at 167 K on cooling. According to the X-ray diffraction, the compound shows R3[combining macron] symmetry at 293 K and triclinic P1[combining macron] symmetry at 110 K. The DMA(+) cations are dynamically disordered in the high-temperature phase and the phase transition is associated with ordering of the DMA(+) cations and distortion of the metal formate framework. The dielectric studies reveal pronounced dielectric dispersion that can be attributed to slow dynamics of the DMA(+) cations. Based on the low-temperature magnetic studies, this compound is a weak ferromagnet with a critical temperature 8.5 K.

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“…Therefore, the materials of metal-organic frameworks (MOFs) with versatile functionalities are vastly investigated in view of their intriguing potential applications in electrically controllable microwave elements, data storage, signal processing, switchable dielectric devices, magnetic-field sensors and spintronic devices. [12][13][14][15][16][17][18] Compared with conventional pure inorganic or organic compounds, AMFFs taking advantage of the structural malleability and modulation to develop polarizable molecular materials could display a variety of physical properties and critical phenomena or phase transitions. [3][4][5][6][7][8] Besides, the organic ligands employed mainly include the monoatomic I À , diatomic CN À , and multiatomic HCOO À , N 3 À anions, which usually act as monovalent end-to-end bridging ligands.…”

Section: Introductionmentioning

confidence: 99%

A prominent dielectric material with extremely high-temperature and reversible phase transition in the high thermally stable perovskite-like architecture

et al. 2015

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A perovskite-like dielectric material, (C 3 N 2 H 5 )Á[Mn(HCOO) 3 ] (1), exhibiting remarkably high T c (phase transition temperature) and pronounced dielectric anomaly, can be considered as a model of novel extremely high-temperature dielectric materials. The systematic characterizations, including detailed differential scanning calorimetry (DSC), variable-temperature single crystal X-ray and X-ray powder diffraction analyses, variable-temperature IR spectra as well as temperature-dependence and frequencydependence dielectric measurements, reveal a sharp structural phase transition from tetragonal P % 42 1 m at the HTP (high temperature phase) to monoclinic P2 1 /c at the RTP (room temperature phase) and the mechanism of dielectric and thermal anomalies can be ascribed to the host-guest interaction coupled with the order-disorder transitions of the Mn(HCOO) 3 À cage and the [(C 3 N 2 H 5 )] + guest, which is the result of a synergistic effect. Emphatically, the T c (438 K) is the highest reported so far for a moleculebased dielectric material (the T c is below room temperature for the most known formate series perovskite-like dielectrics), which makes 1 a promising candidate for molecule-based dramatically hightemperature dielectric materials and may open up new possibilities to make a large breakthrough in the potential practical applications in sensing, dielectric devices, energy storage, data storage and molecular or flexible multifunctional electronic devices.

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First-order structural transition in the multiferroic perovskite-like formate [(CH3)2NH2][Mn(HCOO)3]

Cited by 83 publications

References 34 publications

Raman and IR Studies of Pressure- and Temperature-Induced Phase Transitions in [(CH₂)₃NH₂][Zn(HCOO)₃]

Raman and IR Studies of Pressure- and Temperature-Induced Phase Transitions in [(CH₂)₃NH₂][Zn(HCOO)₃]

Synthesis and order–disorder transition in a novel metal formate framework of [(CH₃)₂NH₂]Na_0.5Fe_0.5(HCOO)₃]

A prominent dielectric material with extremely high-temperature and reversible phase transition in the high thermally stable perovskite-like architecture

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First-order structural transition in the multiferroic perovskite-like formate [(CH3)2NH2][Mn(HCOO)3]

Cited by 83 publications

References 34 publications

Raman and IR Studies of Pressure- and Temperature-Induced Phase Transitions in [(CH2)3NH2][Zn(HCOO)3]

Raman and IR Studies of Pressure- and Temperature-Induced Phase Transitions in [(CH2)3NH2][Zn(HCOO)3]

Synthesis and order–disorder transition in a novel metal formate framework of [(CH3)2NH2]Na0.5Fe0.5(HCOO)3]

A prominent dielectric material with extremely high-temperature and reversible phase transition in the high thermally stable perovskite-like architecture

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Product

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Raman and IR Studies of Pressure- and Temperature-Induced Phase Transitions in [(CH₂)₃NH₂][Zn(HCOO)₃]

Raman and IR Studies of Pressure- and Temperature-Induced Phase Transitions in [(CH₂)₃NH₂][Zn(HCOO)₃]

Synthesis and order–disorder transition in a novel metal formate framework of [(CH₃)₂NH₂]Na_0.5Fe_0.5(HCOO)₃]