Breathing Behaviour Modification of Gallium MIL‐53 Metal–Organic Frameworks Induced by the Bridging Framework Inorganic Anion

A. R. Bonity J. Lutton‐Gething, Lynda T. Nangkam, Jens O. W. Johansson, Ioanna Pallikara, Jonathan M. Skelton, George F. S. Whitehead, Inigo Vitorica‐Yrezabal, Martin P. Attfield

Research output: Contribution to journalArticlepeer-review

Abstract

Controlling aspects of the μ2-X− bridging anion in the metal–organic framework Ga-MIL-53 [GaX(bdc)] (X−=(OH)− or F−, bdc=1, 4-benzenedicarboxylate) is shown to direct the temperature at which thermally induced breathing transitions of this framework occur. In situ single crystal X-ray diffraction studies reveal that substituting 20 % of (OH)− in [Ga(OH)(bdc)] (1) for F− to produce [Ga(OH)0.8F0.2(bdc)] (2) stabilises the large pore (lp) form relative to the narrow pore (np) form, causing a well-defined decrease in the onset of the lp to np transition at higher temperatures, and the adsorption/desorption of nitrogen at lower temperatures through np to lp to intermediate (int) pore transitions. These in situ diffraction studies have also yielded a more plausible crystal structure of the int-[GaX(bdc)] ⋅ H2O phases and shown that increasing the heating rate to a flash heating regime can enable the int-[GaX(bdc)] ⋅ H2O to lp-[GaX(bdc)] transition to occur at a lower temperature than np-[GaX(bdc)] via an unreported pathway.
Original languageEnglish
JournalChemistry – A European Journal
Volume29
Issue number21
Early online date19 Jan 2023
DOIs
Publication statusPublished - 13 Apr 2023

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