Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift

Alice Burnstead, David Cordes, Daniel Dawson, Krisina Chakarova, Mihail Mihaylov, Claire Hobday, Tina Duren, Konstantin Hadjiivanov, Alexandra M.z. Slawin, Sharon E. Ashbrook, Ram Prasad, Paul A. Wright

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Abstract

A fully interpenetrated 8,3-connected zirconium MOF with the the-i topology type, STA-26 (St Andrews porous material-26), has been prepared using the 4,4′,4“-(2,4,6-trimethylbenzene-1,3,5-triyl)tribenzoate (TMTB) tritopic linker with formic acid as a modulating agent. In the as-prepared form STA-26 possesses Im (Formula presented.) m symmetry compared with the Pm (Formula presented.) m symmetry of the non-interpenetrated analogue, NU-1200, prepared using benzoic acid as a modulator. Upon removal of residual solvent there is a shift between the interpenetrating lattices and a resultant symmetry change to Cmcm which is fully reversible. This is observed by X-ray diffraction and 13C MAS NMR is also found to be remarkably sensitive to the structural transition. Furthermore, heating STA-26(Zr) in vacuum dehydroxylates the Zr 6 nodes leaving coordinatively unsaturated Zr 4+ sites, as shown by IR spectroscopy using CO and CD 3CN as probe molecules. Nitrogen adsorption at 77 K together with grand canonical Monte Carlo simulations confirms a microporous, fully interpenetrated, structure with pore volume 0.53 cm 3 g −1 while CO 2 adsorption at 196 K reaches 300 cm 3 STP g −1 at 1 bar. While the pore volume is smaller than that of its non-interpenetrated mesoporous analogue, interpenetration makes the structure more stable to moisture adsorption and introduces shape selectivity in adsorption.

Original languageEnglish
Pages (from-to)6115-6126
Number of pages12
JournalChemistry - A European Journal
Volume24
Issue number23
Early online date31 Jan 2018
DOIs
Publication statusPublished - 20 Apr 2018

Keywords

  • hafnium
  • metal-organic frameworks
  • modulators
  • reversible lattice shift
  • zirconium

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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    Burnstead, A., Cordes, D., Dawson, D., Chakarova, K., Mihaylov, M., Hobday, C., Duren, T., Hadjiivanov, K., Slawin, A. M. Z., Ashbrook, S. E., Prasad, R., & Wright, P. A. (2018). Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift. Chemistry - A European Journal, 24(23), 6115-6126. https://doi.org/10.1002/chem.201705136