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

DOI: 10.1039/D3SC00904A DOI Help

Authors: Alexander J. R. Thom (University of Glasgow) , Gemma F. Turner (The University of Western Australia) , Zachary H. Davis (University of St Andrews) , Martin R. Ward (University of Strathclyde) , Ignas Pakamore (The University of Glasgow) , Claire L. Hobday (The University of Edinburgh) , David R. Allan (Diamond Light Source) , Mark R. Warren (Diamond Light Source) , Wai L. W. Leung (University of Glasgow) , Iain D. H. Oswald (University of Strathclyde) , Russell E. Morris (University of St Andrews) , Stephen A. Moggach (The University of Western Australia) , Sharon E. Ashbrook (University of St Andrews) , Ross S. Forgan (University of Glasgow)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Science

State: Published (Approved)
Published: June 2023
Diamond Proposal Number(s): 24020

Open Access Open Access

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.

Subject Areas: Materials, Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 28/06/2023 10:46


Discipline Tags:

Chemistry Materials Science Chemical Engineering Engineering & Technology Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)