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

doi:10.1039/c8cp03788d

Heterometallic perovskite-type metal-organic framework with an ammonium cation: Structure, phonons, and optical response of [NH₄]Na_0.5Cr_:XAl_{0.5- x}(HCOO)₃ (x = 0, 0.025 and 0.5)

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

Department of Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

17 Citations (Scopus)

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][Na_0.5Cr_0.5(HCOO)₃] (AmNaCr) and [NH₄][Na_0.5Al_0.475Cr_0.025(HCOO)₃] (AmNaAlCr) in comparison to the previously reported [NH₄][Na_0.5Al_0.5(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 language	English
Pages (from-to)	22284-22295
Number of pages	12
Journal	Physical Chemistry Chemical Physics
Volume	20
Issue number	34
DOIs	https://doi.org/10.1039/c8cp03788d
Publication status	Published - 2018

Bibliographical note

Funding Information:
K. L. S. and A. W. are funded by ERC programme grant no. 277757 and the Royal Society. The authors acknowledge computing support from the UK national supercomputing service (Archer), via membership of the UK Materials Chemistry Consortium which is funded by EPSRC (EP/L000202).

Funding Information:
This research was supported by the National Science Centre (NCN) in Poland under project No. DEC-2015/17/D/ST5/01339.

Publisher Copyright:
© 2018 the Owner Societies.

All Science Journal Classification (ASJC) codes

Physics and Astronomy(all)
Physical and Theoretical Chemistry

Access to Document

10.1039/c8cp03788d

Cite this

@article{46ea5758d9da48e0b25e9238b7dda321,

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 Stefa{\'n}ska and Anna Gagor and Svane, {Katrine L.} and Aron Walsh and Waldeci Paraguassu",

note = "Funding Information: K. L. S. and A. W. are funded by ERC programme grant no. 277757 and the Royal Society. The authors acknowledge computing support from the UK national supercomputing service (Archer), via membership of the UK Materials Chemistry Consortium which is funded by EPSRC (EP/L000202). Funding Information: This research was supported by the National Science Centre (NCN) in Poland under project No. DEC-2015/17/D/ST5/01339. Publisher Copyright: {\textcopyright} 2018 the Owner Societies.",

year = "2018",

doi = "10.1039/c8cp03788d",

language = "English",

volume = "20",

pages = "22284--22295",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

number = "34",

}

Heterometallic perovskite-type metal-organic framework with an ammonium cation: Structure, phonons, and optical response of [NH₄]Na_0.5Cr_:XAl_{0.5- x}(HCOO)₃ (x = 0, 0.025 and 0.5). / Ptak, Maciej; Stefańska, Dagmara; Gagor, Anna et al.
In: Physical Chemistry Chemical Physics, Vol. 20, No. 34, 2018, p. 22284-22295.

Research output: Contribution to journal › Article › peer-review

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

N1 - Funding Information: K. L. S. and A. W. are funded by ERC programme grant no. 277757 and the Royal Society. The authors acknowledge computing support from the UK national supercomputing service (Archer), via membership of the UK Materials Chemistry Consortium which is funded by EPSRC (EP/L000202). Funding Information: This research was supported by the National Science Centre (NCN) in Poland under project No. DEC-2015/17/D/ST5/01339. Publisher Copyright: © 2018 the Owner Societies.

PY - 2018

Y1 - 2018

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.

AB - 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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U2 - 10.1039/c8cp03788d

DO - 10.1039/c8cp03788d

M3 - Article

C2 - 30123897

AN - SCOPUS:85052841567

SN - 1463-9076

VL - 20

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JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

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