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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Abstract
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 |
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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. |
Status: | Published |
Refereed: | Yes |
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 |
Publisher: | Wiley |
ISSN: | 0947-6539 |
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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