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Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework

Nature Chemistry volume 1, pages 289–294 (2009)Cite this article

Abstract

Metal organic frameworks (MOFs) are among the most exciting materials discovered recently, attracting particular attention for their gas-adsorption and -storage properties. Certain MOFs show considerable structural flexibility in response to various stimuli. Although there are several examples of ‘breathing’ MOFs, in which structural changes occur without any bond breaking, examples of transformations in which several bonds are broken and made are much rarer. In this paper we demonstrate how a flexible MOF, Cu2(OH)(C8H3O7S)(H2O)·2H2O, can be synthesized by careful choice of the organic linker ligand. The flexibility can be controlled by addition of a supplementary coordinating molecule, which increases the thermal stability of the solid sufficiently for direct imaging with electron microscopy to be possible. We also demonstrate that the MOF shows unprecedented low-pressure selectivity towards nitric oxide through a coordination-driven gating mechanism. The chemical control over these behaviours offers new possibilities for the synthesis of MOFs with unusual and potentially exploitable properties.

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Figure 1: The dehydration–rehydration transformations of Cu-SIP-3.
Figure 2: Large changes in coordination and connectivity on removal of coordinated water (shown as pink spheres).
Figure 3: The structure and electron microscopy of Cu-SIP-3-pyridine·H2O.
Figure 4: Adsorption isotherms for the dehydrated Cu-SIP-3 structure for a variety of atmospheres.

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Acknowledgements

We acknowledge funding from the Engineering and Physical Sciences Research Council and the gas-enabled medical interventions (GEMI) fund. R.E.M. is a Royal Society Wolfson Merit Award holder.

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Authors and Affiliations

  1. EaStChem School of Chemistry, University of St Andrews, Purdie Building, St Andrews, KY16 9ST, UK

    Bo Xiao, Peter J. Byrne, Paul S. Wheatley, David S. Wragg, Wuzong Zhou & Russell E. Morris

  2. Northern Carbon Research Laboratories, Sir Joseph Swan Institute and School of Chemical Engineering and Advanced Material, Bedson Building

    Xuebo Zhao, Ashleigh J. Fletcher & K. Mark Thomas

  3. Newcastle University, Newcastle upon Tyne, NE1 7RU, UK

    Xuebo Zhao, Ashleigh J. Fletcher & K. Mark Thomas

  4. Department of Chemistry, University of Durham Science Laboratories, South Road, Durham, DH1 3LE, UK

    Lars Peters & John S. O. Evans

  5. Synchrotron Radiation Source, Daresbury Laboratory, Daresbury, WA4 4AD, Warrington, UK

    John E. Warren

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Contributions

B.X. and R.E.M conceived and designed the experiments, B.X. completed the synthesis, P.S.W, P.J.B., D.S.W and J.E.W performed the single-crystal diffraction, L.P and J.S.O.E completed the powder-diffraction experiments, B.X., A.J.F., X.Z and K.M.T. completed the adsorption and W.Z. performed the electron microscopy.

Corresponding author

Correspondence to Russell E. Morris.

Supplementary information

Supplementary information

Supplementary information (PDF 2072 kb)

Supplementary information

Crystallographic information for the hydrated form of Cu-SIP-3 (CIF 11 kb)

Supplementary information

Crystallographic information for the dehydrated form of Cu-SIP-3 (CIF 15 kb)

Supplementary information

Crystallographic information for Cu-SIP-3 with coordinated pyridine (CIF 12 kb)

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Xiao, B., Byrne, P., Wheatley, P. et al. Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework. Nature Chem 1, 289–294 (2009). https://doi.org/10.1038/nchem.254

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