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

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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
Issue number34
Publication statusPublished - 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


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