Pressure-induced postsynthetic cluster anion substitution in a MIL-53 topology scandium metal-organic framework

Alexander J. R. Thom, Gemma Turner, Zachary Harry Davis, Martin Ward, Ignas Pakamorė, Clare Hobday, David Allan, Mark Warren, Wai L. W. Leung, Iain D. H. Oswald, Russell Edward Morris, Stephen Moggach*, Sharon E. Ashbrook*, Ross S Forgan*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)
3 Downloads (Pure)

Abstract

Postsynthetic modification of metal-organic frameworks (MOFs) has proven a hugely powerful tool to tune physical properties and introduce functionality, by exploiting reactive sites on both the MOF linkers and their inorganic secondary building units (SBUs), and so has facilitated a wide range of applications. Studies into the reactivity of MOF SBUs have focussed solely on removal of neutral coordinating solvents, or direct exchange of linkers such as carboxylates, despite the prevalence of ancillary charge-balancing oxide and hydroxide ligands found in many SBUs. Herein, we show that the µ2-OH ligands in the MIL-53 topology Sc MOF, GUF-1, are labile, and can be substituted for µ2-OCH3 units through reaction with pore-bound methanol molecules in a very rare example of pressure-induced postsynthetic modification. Using comprehensive solid-state NMR spectroscopic analysis, we show an order of magnitude increase in this cluster anion substitution process after exposing bulk samples suspended in methanol to a pressure of 0.8 GPa in a large volume press. Additionally, single crystals compressed in diamond anvil cells with methanol as the pressure-transmitting medium have enabled full structural characterisation of the process across a range of pressures, leading to a quantitative single-crystal to single-crystal conversion at 4.98 GPa. This unexpected SBU reactivity – in this case chemisorption of methanol – has implications across a range of MOF chemistry, from activation of small molecules for heterogeneous catalysis to chemical stability, and we expect cluster anion substitution to be developed into a highly convenient novel method for modifying the internal pore surface and chemistry of a range of porous materials.
Original languageEnglish
Pages (from-to)7716-7724
Number of pages9
JournalChemical Science
Volume14
Issue number28
Early online date19 Jun 2023
DOIs
Publication statusPublished - 28 Jul 2023

Keywords

  • Solid-state NMR spectroscopy
  • Metal-organic frameworks
  • High-pressure
  • Secondary building unit
  • Postsynthetic modification
  • X-ray crystallography

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