Brammer, L. orcid.org/0000-0001-6435-7197, Ashworth, D., Carrington, E.J. et al. (8 more authors) (2025) Decoupled MOF breathing: pressure‐induced reversal of correlation between orthogonal motions in a diamondoid framework. Angewandte Chemie International Edition. e202504297. ISSN 1433-7851
Abstract
Responsive porous materials can outperform more rigid analogues in applications requiring precise triggering of molecular uptake/release, switching or gradual change in properties. We have uncovered an unprecedented dynamic response in the diamondoid MOF SHF-62, (Me2NH2)[In(BDC-NHC(O)Me)2] (BDC=1,4-benzenedicarboxylate), by using pressure as a stimulus. SHF-62 exhibits two distinct framework “breathing” motions involving changes in (1) cross-section and (2) length of its 1D pores. Our study using synchrotron single-crystal X-ray diffraction in sapphire-capillary (p<0.15 GPa) and diamond-anvil (0.15<p<5 GPa) cells reveals that different pressure regimes trigger positive and negative correlation between these two motions, requiring an unprecedented mechanical decoupling. Specifically, the DMF-solvated framework SHF-62-DMF, in DMF as pressure-transmitting medium, undergoes initial hyperexpansion of pore cross-section (p≤0.9 GPa), due to DMF ingress, followed by reversal/reduction at p>0.9 GPa while pore length contracts for all pressure increases, revealing decoupling of the two framework deformations. By contrast, non-penetrating medium FC-70 imposes correlated compression (p<1.4 GPa) of pore cross-section and length, resembling framework activation/desolvation motions but of greater magnitude. Similar behaviour occurs for SHF-62-CHCl3 in CHCl3 (p<0.14 GPa), suggesting minimal ingress of CHCl3. These findings change our understanding of MOF dynamic responses and provide a platform for future responsive materials development.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2025 The Author(s). This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. http://creativecommons.org/licenses/by/4.0/ |
Keywords: | Metal-Organic Framework; high pressure; flexibility; switching; in situ diffraction |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > School of Mathematical and Physical Sciences |
Funding Information: | Funder Grant number ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL EP/T034068/1 |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 09 May 2025 09:41 |
Last Modified: | 20 May 2025 09:35 |
Status: | Published online |
Publisher: | Wiley |
Refereed: | Yes |
Identification Number: | 10.1002/anie.202504297 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:226475 |