Controlling the flexibility of MIL-88A(Sc) through synthetic optimisation and postsynthetic halogenation

Walshe, C., Thom, A. J. R. , Wilson, C. , Ling, S. and Forgan, R. S. (2022) Controlling the flexibility of MIL-88A(Sc) through synthetic optimisation and postsynthetic halogenation. Chemistry: A European Journal, 28(48), e202201364. (doi: 10.1002/chem.202201364) (PMID:35647658)

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Breathing behaviour in metal-organic frameworks (MOFs), the distinctive transformation between a porous phase and a less (or non) porous phase, often controls the uptake of guest molecules, endowing flexible MOFs with highly selective gas adsorptive properties . In highly flexible topologies, breathing can be tuned by linker modification, which is typically achieved pre-synthetically by the use of functionalised linkers. Herein, we show that MIL-88A(Sc) exhibits the characteristic flexibility of its topology, which can be tuned by (i) modifying synthetic conditions to yield a formate-buttressed analogue that is rigid and porous, and (ii) postsynthetic bromination across the alkene functionality of the fumarate ligand, generating a product that is rigid but non-porous. As well as providing different methodologies for tuning the flexibility and breathing behaviour of this archetypal MOF, we show that bromination of the formate-bridged analogue results in an identical material, representing a rare example of two different MOFs being postsynthetically converted to the same end product.

Item Type:Articles
Additional Information:We thank the Royal Society for a University Research Fellowship (UF160394) and a Research Fellows Enhancement Award (RGF \EA\180077), and the EPSRC for funding (EP/N509668/1). We acknowledge the use of the ARCHER2 supercomputer through membership of the UK’s HPC Materials Chemistry Consortium, which is funded by EPSRC grant number EP/R02943.
Glasgow Author(s) Enlighten ID:Forgan, Professor Ross and Thom, Mr Alexander and Wilson, Dr Claire and Walshe, Miss Catherine
Authors: Walshe, C., Thom, A. J. R., Wilson, C., Ling, S., and Forgan, R. S.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
ISSN (Online):1521-3765
Published Online:01 June 2022
Copyright Holders:Copyright © 2022 The Authors
First Published:First published in Chemistry: A European Journal 28(48): e202201364
Publisher Policy:Reproduced under a Creative Commons licence

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
172865EPSRC DTP 16/17 and 17/18Mary Beth KneafseyEngineering and Physical Sciences Research Council (EPSRC)EP/N509668/1Research and Innovation Services
300319Engineering Metal-Organic Frameworks as Artificial EnzymesRoss ForganThe Royal Society (ROYSOC)UF160394Chemistry
301732Radical Chemisorption in Metal-Organic Frameworks for Functionalisation and PurificationRoss ForganThe Royal Society (ROYSOC)RGF\EA\180077Chemistry