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Mechanical gas capture and release in a network solid via multiple single-crystalline transformations

Nature Materials volume 7, pages 229–235 (2008)Cite this article

Abstract

Metal–organic frameworks have demonstrated functionality stemming from both robustness and pliancy and as such, offer promise for a broad range of new materials. The flexible aspect of some of these solids is intriguing for so-called ‘smart’ materials in that they could structurally respond to an external stimulus. Herein, we present an open-channel metal–organic framework that, on dehydration, shifts structure to form closed pores in the solid. This occurs through multiple single-crystal-to-single-crystal transformations such that snapshots of the mechanism of solid-state conversion can be obtained. Notably, the gas composing the atmosphere during dehydration becomes trapped in the closed pores. On rehydration, the pores open to release the trapped gas. Thus, this new material represents a thermally robust and porous material that is also capable of dynamically capturing and releasing gas in a controlled manner.

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Figure 1: Single-crystal X-ray structures of fully hydrated 1, intermediates 2a and 3, and dehydrated 4.
Figure 2: X-ray diffraction images of a single crystal of 1 undergoing heating while on the diffractometer.
Figure 3: Single crystals of 4.
Figure 4: Hyperpolarized 129Xe NMR of a sample of 1 on drying.
Figure 5: Accessibility of the pores in 4 to spheres of different radii representing different gases as modelled in atoms.
Figure 6: Release of NH3 from 4 on rehydration.

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Acknowledgements

D.T.C. and G.K.H.S. thank the Natural Sciences and Engineering Research Council (NSERC) of Canada.

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Authors and Affiliations

  1. Department of Chemistry, University of Calgary, Calgary, Alberta, T2N 1N4, Canada

    Brett D. Chandler, David T. Cramb & George K. H. Shimizu

  2. Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa Ontario, K1A 0R6, Canada

    Gary D. Enright, Konstantin A. Udachin, Shane Pawsey & John A. Ripmeester

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Correspondence to David T. Cramb or George K. H. Shimizu.

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Chandler, B., Enright, G., Udachin, K. et al. Mechanical gas capture and release in a network solid via multiple single-crystalline transformations. Nature Mater 7, 229–235 (2008). https://doi.org/10.1038/nmat2101

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