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Solvent-switchable continuous-breathing behaviour in a diamondoid metal–organic framework and its influence on CO2 versus CH4 selectivity

Nature Chemistry volume 9, pages 882–889 (2017)Cite this article

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Abstract

Understanding the behaviour of flexible metal–organic frameworks (MOFs)—porous crystalline materials that undergo a structural change upon exposure to an external stimulus—underpins their design as responsive materials for specific applications, such as gas separation, molecular sensing, catalysis and drug delivery. Reversible transformations of a MOF between open- and closed-pore forms—a behaviour known as ‘breathing’—typically occur through well-defined crystallographic transitions. By contrast, continuous breathing is rare, and detailed characterization has remained very limited. Here we report a continuous-breathing mechanism that was studied by single-crystal diffraction in a MOF with a diamondoid network, (Me2NH2)[In(ABDC)2] (ABDC, 2-aminobenzene-1,4-dicarboxylate). Desolvation of the MOF in two different solvents leads to two polymorphic activated forms with very different pore openings, markedly different gas-adsorption capacities and different CO2 versus CH4 selectivities. Partial desolvation introduces a gating pressure associated with CO2 adsorption, which shows that the framework can also undergo a combination of stepped and continuous breathing.

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Figure 1: Crystal structure of SHF-61.
Figure 2: Gas adsorption by SHF-61.
Figure 3: Continuous breathing of SHF-61 on desolvation, and comparison with other breathing MOFs.
Figure 4: Continuous breathing of SHF-61 on resolvation.
Figure 5: Gated CO2 uptake by partially solvated SHF-61-DMF.
Figure 6: Proposed role of guest–framework interactions in the solvent-dependent continuous-breathing properties of SHF-61.

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Acknowledgements

We are grateful to the Engineering and Physical Sciences Research Council for funding of the E-Futures Doctoral Training Centre (grant EP/G037477/1) and a Doctoral Prize fellowship for E.J.C. We thank Diamond Light Source for beam time at beamlines I19 and I11.

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Authors and Affiliations

  1. Department of Chemistry, University of Sheffield, Brook Hill, Sheffield, S3 7HF, UK

    Elliot J. Carrington & Lee Brammer

  2. Department of Chemical and Process Engineering, University of Strathclyde, 75 Montrose Street, Glasgow, G1 1XJ, UK

    Craig A. McAnally & Ashleigh J. Fletcher

  3. Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK

    Stephen P. Thompson & Mark Warren

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  1. Elliot J. Carrington
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Contributions

L.B. and E.J.C. conceived the project. E.J.C. carried out the syntheses and analysis of single-crystal and powder X-ray diffraction data. C.A.M. and A.J.F. conducted gravimetric and volumetric gas-adsorption measurements and analyses. M.W. and S.P.T. provided the experimental set-ups and support for the in situ synchrotron crystallographic measurements and data analysis. L.B. was responsible for the overall direction of the project. L.B. and E.J.C. prepared the manuscript and all of the other authors contributed to its discussion.

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Correspondence to Lee Brammer.

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Supplementary information

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Supplementary information (PDF 3082 kb)

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Crystallographic data for compound A1. (CIF 1343 kb)

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Crystallographic data for compound A2. (CIF 950 kb)

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Crystallographic data for compound A3. (CIF 1570 kb)

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Crystallographic data for compound C1. (CIF 1262 kb)

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Crystallographic data for compound C2. (CIF 859 kb)

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Crystallographic data for compound C3. (CIF 623 kb)

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Crystallographic data for compound C4. (CIF 838 kb)

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Crystallographic data for compound C5. (CIF 658 kb)

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Crystallographic data for compound C6. (CIF 656 kb)

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Crystallographic data for compound C7. (CIF 692 kb)

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Crystallographic data for compound D1.6. (CIF 474 kb)

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Crystallographic data for compound D2.2. (CIF 467 kb)

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Crystallographic data for compound F1. (CIF 569 kb)

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Crystallographic data for compound F2. (CIF 483 kb)

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Crystallographic data for compound F3. (CIF 516 kb)

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Crystallographic data for compound N1.1. (CIF 942 kb)

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Crystallographic data for compound N1.2. (CIF 521 kb)

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Crystallographic data for compound N1.4. (CIF 625 kb)

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Crystallographic data for compound N1.5. (CIF 645 kb)

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Carrington, E., McAnally, C., Fletcher, A. et al. Solvent-switchable continuous-breathing behaviour in a diamondoid metal–organic framework and its influence on CO2 versus CH4 selectivity. Nature Chem 9, 882–889 (2017). https://doi.org/10.1038/nchem.2747

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