Decoupled MOF Breathing: Pressure-Induced Reversal of Correlation between Orthogonal Motions in a Diamondoid Framework

David Ashworth; Elliot J. Carrington; Thomas M. Roseveare; Charles J. McMonagle; Martin R  Ward; Ashleigh J Fletcher; Tina Düren; Mark R Warren; Stephen Moggach; Iain D. H.  Oswald; Lee Brammer

doi:10.1002/anie.202504297

Decoupled MOF Breathing: Pressure-Induced Reversal of Correlation between Orthogonal Motions in a Diamondoid Framework

David Ashworth, Elliot J. Carrington, Thomas M. Roseveare, Charles J. McMonagle, Martin R Ward, Ashleigh J Fletcher, Tina Düren, Mark R Warren, Stephen Moggach, Iain D. H. Oswald, Lee Brammer

Research output: Contribution to journal › Article › peer-review

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, (Me ₂NH ₂)[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, nonpenetrating 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 behavior occurs for SHF-62-CHCl ₃ in CHCl ₃ (p < 0.14 GPa), suggesting minimal ingress of CHCl ₃. These findings change our understanding of MOF dynamic responses and provide a platform for future responsive materials development.

Original language	English
Article number	e202504297
Journal	Angewandte Chemie International Edition
Early online date	28 Apr 2025
DOIs	https://doi.org/10.1002/anie.202504297
Publication status	E-pub ahead of print - 28 Apr 2025

Data Availability Statement

Data underpinning this publication are openly available from the University of Strathclyde KnowledgeBase at https://doi.org/10.15129/acde92cc-96ae-4234-ace4-2164a407e5d1.

Funding

The authors are grateful to the Engineering and Physical Science Research Council (EPSRC) for funding of the E\u2010Futures Doctoral Training Centre (grant EP/G037477/1) and a Doctoral Prize fellowship for E.J.C. The authors also thank the EPSRC for funding that has supported D.J.A. and T.M.R. (grants EP/T034114/1, EP/T034068/1 and EP/T034130/1). The authors acknowledge Diamond Light Source for providing funding for a PhD studentship for C.J.M., as well as time and staff support on beamline I19 under proposals MT13958\u20101, MT15190\u20101, and CY29038\u20101.

Funders	Funder number
Engineering and Physical Sciences Research Council	EP/G037477/1, EP/T034114/1 , EP/T034068/1 , EP/T034130/1
E‐Futures Doctoral Training Centre	EP/T034114/1, EP/G037477/1, EP/T034130/1, EP/T034068/1

Keywords

Breathing
High pressure
In-situ diffraction
Metal-organic framework
Switching

ASJC Scopus subject areas

Catalysis
General Chemistry

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Ashworth, D., Carrington, E. J., Roseveare, T. M., McMonagle, C. J., Ward, M. R., Fletcher, A. J., Düren, T., Warren, M. R., Moggach, S., Oswald, I. D. H., & Brammer, L. (2025). Decoupled MOF Breathing: Pressure-Induced Reversal of Correlation between Orthogonal Motions in a Diamondoid Framework. Angewandte Chemie International Edition, Article e202504297. Advance online publication. https://doi.org/10.1002/anie.202504297

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title = "Decoupled MOF Breathing: Pressure-Induced Reversal of Correlation between Orthogonal Motions in a Diamondoid Framework",

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, (Me 2NH 2)[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, nonpenetrating 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 behavior occurs for SHF-62-CHCl 3 in CHCl 3 (p < 0.14 GPa), suggesting minimal ingress of CHCl 3. These findings change our understanding of MOF dynamic responses and provide a platform for future responsive materials development.",

keywords = "Breathing, High pressure, In-situ diffraction, Metal-organic framework, Switching",

author = "David Ashworth and Carrington, {Elliot J.} and Roseveare, {Thomas M.} and McMonagle, {Charles J.} and Ward, {Martin R} and Fletcher, {Ashleigh J} and Tina D{\"u}ren and Warren, {Mark R} and Stephen Moggach and Oswald, {Iain D. H.} and Lee Brammer",

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T2 - Pressure-Induced Reversal of Correlation between Orthogonal Motions in a Diamondoid Framework

AU - Ashworth, David

AU - Carrington, Elliot J.

AU - Roseveare, Thomas M.

AU - McMonagle, Charles J.

AU - Ward, Martin R

AU - Fletcher, Ashleigh J

AU - Düren, Tina

AU - Warren, Mark R

AU - Moggach, Stephen

AU - Oswald, Iain D. H.

AU - Brammer, Lee

PY - 2025/4/28

Y1 - 2025/4/28

N2 - 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, (Me 2NH 2)[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, nonpenetrating 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 behavior occurs for SHF-62-CHCl 3 in CHCl 3 (p < 0.14 GPa), suggesting minimal ingress of CHCl 3. These findings change our understanding of MOF dynamic responses and provide a platform for future responsive materials development.

AB - 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, (Me 2NH 2)[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, nonpenetrating 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 behavior occurs for SHF-62-CHCl 3 in CHCl 3 (p < 0.14 GPa), suggesting minimal ingress of CHCl 3. These findings change our understanding of MOF dynamic responses and provide a platform for future responsive materials development.

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KW - High pressure

KW - In-situ diffraction

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DO - 10.1002/anie.202504297

M3 - Article

SN - 1433-7851

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

M1 - e202504297

ER -

Decoupled MOF Breathing: Pressure-Induced Reversal of Correlation between Orthogonal Motions in a Diamondoid Framework

Abstract

Data Availability Statement

Funding

Keywords

ASJC Scopus subject areas

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