Temperature-dependent IR and Raman studies of metal–organic frameworks [(CH3)2NH2][M(HCOO)3], M=Mg and Cd

Szymborska-Małek, Katarzyna; Trzebiatowska, Monika; Mączka, Mirosław; Gągor, Anna

doi:10.1016/j.saa.2016.01.031

Cited by 33 publications

(23 citation statements)

References 21 publications

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“…The observed wavenumbers along with the assignment are given in Table . We propose the assignment of bands corresponding to internal vibrations of the HCOO − and EtA + ions based mainly on the data available for the related formates with NH 4 + ([NH 4 ][Mg(HCOO) 3 ]), DMA + ([(CH 3 ) 2 NH 2 ][Mg(HCOO) 3 ]) and EtA + cations, ([CH 3 CH 2 NH 3 ][Na 0.5 M III 0.5 (HCOO) 3 ] (M III = Al, Cr, Fe), [CH 3 CH 2 NH 3 ] 2 [Fe II Fe III (HCOO) 6 ], and [CH 3 CH 2 NH 3 ][Cd(HCOO) 3 ]) . Because the room temperature phonon properties of EtACd and EtAMn have been reported recently by us, the detailed description will be avoided here.…”

Section: Resultsmentioning

confidence: 99%

“…These bands shift towards higher wavenumbers when heavier Mn II or Cd II ions are replaced by lighter Mg II ions. According to the literature data, librations of formate ions are usually observed as strong Raman bands and weak or medium intensity IR bands; therefore, we assigned the bands in the 92–198 cm −1 spectral range to L(HCOO − ) modes and those below 80 cm −1 to T′ and L modes of the EtA + ions (Fig. b).…”

Section: Resultsmentioning

confidence: 99%

“…The observed wavenumbers along with the assignment are given in Table 1 3 ]). [21,[34][35][36][37][38] Because the room temperature phonon properties of EtACd and EtAMn have been reported recently by us, [21] the detailed description will be avoided here. However, we would like to highlight the importance of metal cation size on vibrational properties of HCOO À ions.…”

Section: Crystal Structuresmentioning

confidence: 99%

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Vibrational investigation of pressure‐ and temperature‐induced phase transitions in metal formates templated by ethylammonium ions

Ciupa

Ptak

Mączka

et al. 2017

J Raman Spectroscopy

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We report for the first time phonon properties of [CH3CH2NH3][Mg(HCOO)3] (EtAMg). The studied compound undergoes two structural temperature‐induced phase transitions and temperature‐dependent Raman and infrared studies let us to obtain insight into mechanism of these transitions. In particular, very large broadening of infrared and Raman bands, attributed to vibrations of the NH3 groups, revealed highly dynamic nature of these groups in the both high‐temperature phases. This result indicates that the phase transitions at 374 and 426 K are associated with disordering of the template cations. Raman and infrared data also show that both phase transitions are accompanied by significant distortion of the anionic framework. We also present the pressure‐dependent Raman data of EtAMn framework up to 7.1 GPa. These data revealed presence of two pressure‐induced phase transitions, one between 3.7 and 4.0 GPa and second between 5.6 and 6.0 GPa. We discuss mechanisms of these transitions. Copyright © 2017 John Wiley & Sons, Ltd.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Crystal Structuresmentioning

confidence: 99%

See 1 more Smart Citation

Vibrational investigation of pressure‐ and temperature‐induced phase transitions in metal formates templated by ethylammonium ions

Ciupa

Ptak

Mączka

et al. 2017

J Raman Spectroscopy

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“…So far, vibrational spectroscopy was mainly employed to monitor macroscopic properties of MOFs/COFs such as structure and stability under varied conditions. The vibrational fingerprints from the materials' organic building can be used to probe structural alterations (Ciupa and Ptak , Szymborska‐Małek et al ) or phase transitions (Mączka et al , Kumari et al ). Moreover, FTIR and Raman spectroscopy have been used for studying interactions/inclusions of small molecules such as hydrogen, water as well as CO 2 within MOFs (Nijem et al ,b).…”

Section: Vibrational Spectroscopy For Studying Reaction Mechanisms Wimentioning

confidence: 99%

Artificial photosynthesis with metal and covalent organic frameworks (MOFs and COFs): challenges and prospects in fuel‐forming electrocatalysis

Heidary

Harris

et al. 2019

Physiologia Plantarum

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Mimicking photosynthesis in generating chemical fuels from sunlight is a promising strategy to alleviate society's demand for fossil fuels. However, this approach involves a number of challenges that must be overcome before this concept can emerge as a viable solution to society's energy demand. Particularly in artificial photosynthesis, the catalytic chemistry that converts energy in the form of electricity into carbon‐based fuels and chemicals has yet to be developed. Here, we describe the foundational work and future prospects of an emerging and promising class of materials: metal‐ and covalent‐organic frameworks (MOFs and COFs). Within this context, these porous and tuneable framework materials have achieved initial success in converting abundant feedstocks (H2O and CO2) into chemicals and fuels. In this review, we first highlight key achievements in this direction. We then follow with a perspective on precisely how MOFs and COFs can perform in ways not possible with conventional molecular or heterogeneous catalysts. We conclude with a view on how spectroscopically probing MOF and COF catalysis can be used to elucidate reaction mechanisms and material dynamics throughout the course of reaction.

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“…Going by the above observation, one could infer that the onset of H-bonded interaction alone does not always spontaneously result in the cooperative structural collapse. Framework flexibility [6,13,14,17,18] and cation size effects [13,14] are also said to play an important role in influencing the phase transition in these systems.…”

Section: Formate-related Modesmentioning

confidence: 99%

Raman spectroscopic studies across the ferroelectric transition in cobalt substituted dimethyl amine manganese formate

Premila

Bharathi

Rajaraman

et al. 2018

J Raman Spectroscopy

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Temperature‐dependent Raman studies, across the ferroelectric transition, Tc, in the metal organic framework material, [(CH3)2NH2][Mn(HCOO)3]—DMMn, and its cobalt (Co) doped analogues have been carried out to look for the changes in the lattice and intramolecular modes associated with the orientational ordering of the central dimethyl ammonium cation (DMA+) driven by the hydrogen‐bonded interaction between the DMA cation and the formate anion. A systematic decrease of the transition temperature with increased Co doping has been observed that correlates with results of specific heat measurements. The low‐wavenumber librational mode of the DMA cation shows a dramatic softening and narrowing of line width, across the transition, providing direct evidence of the slowing down of the rotation of the DMA cation associated with the orientational ordering. The evolution with temperature of the N‐H stretch modes of the DMA cation suggests that invoking the hydrogen‐bonding interactions alone is not enough to understand the observed decrease in the ferroelectric transition with Co doping in DMMn. A subtle interplay between the framework flexibility, size/charge of the metal cation, and the hydrogen‐bonding tendency finally decides the transition temperature in these materials.

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Temperature-dependent IR and Raman studies of metal–organic frameworks [(CH3)2NH2][M(HCOO)3], M=Mg and Cd

Cited by 33 publications

References 21 publications

Vibrational investigation of pressure‐ and temperature‐induced phase transitions in metal formates templated by ethylammonium ions

Vibrational investigation of pressure‐ and temperature‐induced phase transitions in metal formates templated by ethylammonium ions

Artificial photosynthesis with metal and covalent organic frameworks (MOFs and COFs): challenges and prospects in fuel‐forming electrocatalysis

Raman spectroscopic studies across the ferroelectric transition in cobalt substituted dimethyl amine manganese formate

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