Heterometallic perovskite-type metal-organic framework with an ammonium cation

Structure, phonons, and optical response of [NH4]Na0.5Cr:XAl0.5- x(HCOO)3 (x = 0, 0.025 and 0.5)

Maciej Ptak, Dagmara Stefańska, Anna Gagor, Katrine L. Svane, Aron Walsh, Waldeci Paraguassu

Research output: Contribution to journalArticle

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Abstract

We report the synthesis, crystal structure, vibrational and luminescence properties of two heterometallic perovskite-type metal-organic frameworks (MOFs) containing the ammonium cation (NH4 +, Am+): [NH4][Na0.5Cr0.5(HCOO)3] (AmNaCr) and [NH4][Na0.5Al0.475Cr0.025(HCOO)3] (AmNaAlCr) in comparison to the previously reported [NH4][Na0.5Al0.5(HCOO)3] (AmNaAl). The room-temperature crystal structure of AmNaCr and AmNaAlCr was determined to be R3. The hydrogen bonding (HB) energy calculated using density functional theory (DFT) agrees well with experimental data, and confirms the existence of almost identical H-bonding in AmNaCr and AmNaAl, with three short hydrogen bonds and a longer trifurcated H-bond. Temperature-dependent Raman measurements supported by differential scanning calorimetry show that AmNaCr does not undergo any structural phase transitions in the 80-400 K temperature range. The high-pressure Raman spectra of AmNaCr show the onset of two structural instabilities near 0.5 and 1.5 GPa. The first instability involves weak distortion of the framework, while the second leads to irreversible amorphization of the sample. High-pressure DFT simulations show that the unit cell of the AmNaCr compound contracts along the c axis, which leads to a shortening of the trifurcated H-bond. The optical properties show that both studied crystals exhibit Cr3+-based emission characteristic of intermediate ligand field strength.

Original languageEnglish
Pages (from-to)22284-22295
Number of pages12
JournalPhysical Chemistry Chemical Physics
Volume20
Issue number34
DOIs
Publication statusPublished - 2018 Jan 1

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Phonons
Ammonium Compounds
Cations
phonons
Metals
density functional theory
cations
crystal structure
Density functional theory
Hydrogen bonds
Crystal structure
metals
field strength
heat measurement
Amorphization
luminescence
Raman spectra
hydrogen bonds
optical properties
Temperature

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Heterometallic perovskite-type metal-organic framework with an ammonium cation: Structure, phonons, and optical response of [NH4]Na0.5Cr:XAl0.5- x(HCOO)3 (x = 0, 0.025 and 0.5)",
abstract = "We report the synthesis, crystal structure, vibrational and luminescence properties of two heterometallic perovskite-type metal-organic frameworks (MOFs) containing the ammonium cation (NH4 +, Am+): [NH4][Na0.5Cr0.5(HCOO)3] (AmNaCr) and [NH4][Na0.5Al0.475Cr0.025(HCOO)3] (AmNaAlCr) in comparison to the previously reported [NH4][Na0.5Al0.5(HCOO)3] (AmNaAl). The room-temperature crystal structure of AmNaCr and AmNaAlCr was determined to be R3. The hydrogen bonding (HB) energy calculated using density functional theory (DFT) agrees well with experimental data, and confirms the existence of almost identical H-bonding in AmNaCr and AmNaAl, with three short hydrogen bonds and a longer trifurcated H-bond. Temperature-dependent Raman measurements supported by differential scanning calorimetry show that AmNaCr does not undergo any structural phase transitions in the 80-400 K temperature range. The high-pressure Raman spectra of AmNaCr show the onset of two structural instabilities near 0.5 and 1.5 GPa. The first instability involves weak distortion of the framework, while the second leads to irreversible amorphization of the sample. High-pressure DFT simulations show that the unit cell of the AmNaCr compound contracts along the c axis, which leads to a shortening of the trifurcated H-bond. The optical properties show that both studied crystals exhibit Cr3+-based emission characteristic of intermediate ligand field strength.",
author = "Maciej Ptak and Dagmara Stefańska and Anna Gagor and Svane, {Katrine L.} and Aron Walsh and Waldeci Paraguassu",
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publisher = "Royal Society of Chemistry",
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Heterometallic perovskite-type metal-organic framework with an ammonium cation : Structure, phonons, and optical response of [NH4]Na0.5Cr:XAl0.5- x(HCOO)3 (x = 0, 0.025 and 0.5). / Ptak, Maciej; Stefańska, Dagmara; Gagor, Anna; Svane, Katrine L.; Walsh, Aron; Paraguassu, Waldeci.

In: Physical Chemistry Chemical Physics, Vol. 20, No. 34, 01.01.2018, p. 22284-22295.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Heterometallic perovskite-type metal-organic framework with an ammonium cation

T2 - Structure, phonons, and optical response of [NH4]Na0.5Cr:XAl0.5- x(HCOO)3 (x = 0, 0.025 and 0.5)

AU - Ptak, Maciej

AU - Stefańska, Dagmara

AU - Gagor, Anna

AU - Svane, Katrine L.

AU - Walsh, Aron

AU - Paraguassu, Waldeci

PY - 2018/1/1

Y1 - 2018/1/1

N2 - We report the synthesis, crystal structure, vibrational and luminescence properties of two heterometallic perovskite-type metal-organic frameworks (MOFs) containing the ammonium cation (NH4 +, Am+): [NH4][Na0.5Cr0.5(HCOO)3] (AmNaCr) and [NH4][Na0.5Al0.475Cr0.025(HCOO)3] (AmNaAlCr) in comparison to the previously reported [NH4][Na0.5Al0.5(HCOO)3] (AmNaAl). The room-temperature crystal structure of AmNaCr and AmNaAlCr was determined to be R3. The hydrogen bonding (HB) energy calculated using density functional theory (DFT) agrees well with experimental data, and confirms the existence of almost identical H-bonding in AmNaCr and AmNaAl, with three short hydrogen bonds and a longer trifurcated H-bond. Temperature-dependent Raman measurements supported by differential scanning calorimetry show that AmNaCr does not undergo any structural phase transitions in the 80-400 K temperature range. The high-pressure Raman spectra of AmNaCr show the onset of two structural instabilities near 0.5 and 1.5 GPa. The first instability involves weak distortion of the framework, while the second leads to irreversible amorphization of the sample. High-pressure DFT simulations show that the unit cell of the AmNaCr compound contracts along the c axis, which leads to a shortening of the trifurcated H-bond. The optical properties show that both studied crystals exhibit Cr3+-based emission characteristic of intermediate ligand field strength.

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