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CO2-induced single-crystal to single-crystal transformations of an interpenetrated flexible MOF explained by in situ crystallographic analysis and molecular modeling

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Abstract

A molecular-level investigation is reported on breathing behaviour of a metal–organic framework (1) in response to CO2 gas pressure. High-pressure gas adsorption shows a pronounced step corresponding to a gate-opening phase transformation from a closed (1cp) to a large-pore (1lp) form. A plateau is observed upon desorption corresponding to narrow-pore intermediate form 1np which does not occur during adsorption. These events are corroborated by pressure-gradient differential scanning calorimetry and in situ single-crystal X-ray diffraction analysis under controlled CO2 gas pressure. Complete crystallographic characterisation facilitated a rationalisation of each phase transformation in the series 1cp1lp1np1cp during adsorption and subsequent desorption. Metropolis grand-canonical Monte Carlo simulations and DFT-PBE-D3 interaction energy calculations strongly underpin this first detailed structural investigation of an intermediate phase encountered upon desorption.

Graphical abstract: CO2-induced single-crystal to single-crystal transformations of an interpenetrated flexible MOF explained by in situ crystallographic analysis and molecular modeling

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Publication details

The article was received on 13 Aug 2019, accepted on 06 Sep 2019 and first published on 06 Sep 2019


Article type: Edge Article
DOI: 10.1039/C9SC04043A
Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    CO2-induced single-crystal to single-crystal transformations of an interpenetrated flexible MOF explained by in situ crystallographic analysis and molecular modeling

    A. Hazra, D. P. van Heerden, S. Sanyal, P. Lama, C. Esterhuysen and L. J. Barbour, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C9SC04043A

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