Abstract
Organic solids composed by weak van der Waals forces are attracting considerable attention owing to their potential applications in gas storage, separation and sensor applications1. Herein we report a gas-induced transformation that remarkably converts the high-density guest-free form of a well-known organic host (p-tert-butylcalix[4]arene) to a low-density form and vice versa1, a process that would be expected to involve surmounting a considerable energy barrier2. This transformation occurs despite the fact that the high-density form is devoid of channels or pores3. Gas molecules seem to diffuse through the non-porous solid into small lattice voids, and initiate the transition to the low-density kinetic form with ∼10% expansion of the crystalline organic lattice, which corresponds to absorption of CO2 and N2O (refs 45). This suggests the possibility of a more general phenomenon that can be exploited to find more porous materials from non-porous organic and metal–organic frameworks that possess void space large enough to accommodate the gas molecules6,7,8,9,10,11,12,13.
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Acknowledgements
This work was supported in part by Laboratory Directed Research and Development funding. In addition, portions of the work were supported by the US Department of Energy, Office of Energy Efficiency and Office of Fossil Energy. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy under Contract DE-AC05-76RL01830. We thank P. F. Martin and S. D. Barton for gas sorption and solid-state nuclear magnetic resonance measurements. We also thank of one of the referees for thoughts about the mechanism.
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P.K.T. and J.L.A. analysed and interpreted the data from H.T.S. and J.T. H.T.S. and J.T. carried out powder diffraction and single-crystal diffraction experiments. P.K.T., B.P.M., S.J.D. and J.L.A. wrote the paper.
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Thallapally, P., Peter McGrail, B., Dalgarno, S. et al. Gas-induced transformation and expansion of a non-porous organic solid. Nature Mater 7, 146–150 (2008). https://doi.org/10.1038/nmat2097
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DOI: https://doi.org/10.1038/nmat2097
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