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

Autor: Thom AJR; WestCHEM School of Chemistry, University of Glasgow Joseph Black Building, University Avenue Glasgow G12 8QQ UK ross.forgan@glasgow.ac.uk., Turner GF; School of Molecular Sciences, The University of Western Australia 35 Stirling Highway, Crawley Perth Western Australia 6009 Australia stephen.moggach@uwa.edu.au., Davis ZH; EaStCHEM School of Chemistry and Centre of Magnetic Resonance, University of St Andrews St Andrews KY16 9ST UK sema@st-andrews.ac.uk., Ward MR; Strathclyde Institute of Pharmacy & Biomedical Sciences (SIPBS), University of Strathclyde 161 Cathedral Street Glasgow G4 0RE UK., Pakamorė I; WestCHEM School of Chemistry, University of Glasgow Joseph Black Building, University Avenue Glasgow G12 8QQ UK ross.forgan@glasgow.ac.uk., Hobday CL; EaStCHEM School of Chemistry and Centre for Science at Extreme Conditions, The University of Edinburgh King's Buildings, David Brewster Road Edinburgh EH9 3FJ UK., Allan DR; Diamond Light Source Ltd, Harwell Science and Innovation Campus Didcot Oxfordshire OX11 0DE UK., Warren MR; Diamond Light Source Ltd, Harwell Science and Innovation Campus Didcot Oxfordshire OX11 0DE UK., Leung WLW; WestCHEM School of Chemistry, University of Glasgow Joseph Black Building, University Avenue Glasgow G12 8QQ UK ross.forgan@glasgow.ac.uk., Oswald IDH; Strathclyde Institute of Pharmacy & Biomedical Sciences (SIPBS), University of Strathclyde 161 Cathedral Street Glasgow G4 0RE UK., Morris RE; EaStCHEM School of Chemistry and Centre of Magnetic Resonance, University of St Andrews St Andrews KY16 9ST UK sema@st-andrews.ac.uk., Moggach SA; School of Molecular Sciences, The University of Western Australia 35 Stirling Highway, Crawley Perth Western Australia 6009 Australia stephen.moggach@uwa.edu.au., Ashbrook SE; EaStCHEM School of Chemistry and Centre of Magnetic Resonance, University of St Andrews St Andrews KY16 9ST UK sema@st-andrews.ac.uk., Forgan RS; WestCHEM School of Chemistry, University of Glasgow Joseph Black Building, University Avenue Glasgow G12 8QQ UK ross.forgan@glasgow.ac.uk.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2023 Jun 19; Vol. 14 (28), pp. 7716-7724. Date of Electronic Publication: 2023 Jun 19 (Print Publication: 2023).
DOI: 10.1039/d3sc00904a
Abstrakt: Postsynthetic modification of metal-organic frameworks (MOFs) has proven to be 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 μ 2 -OH ligands in the MIL-53 topology Sc MOF, GUF-1, are labile, and can be substituted for μ 2 -OCH 3 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.
Competing Interests: The authors declare no competing interests.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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