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Abstract

Porous materials are important in a wide range of applications including molecular separations and catalysis. We demonstrate that covalently bonded organic cages can assemble into crystalline microporous materials. The porosity is prefabricated and intrinsic to the molecular cage structure, as opposed to being formed by non-covalent self-assembly of non-porous sub-units. The three-dimensional connectivity between the cage windows is controlled by varying the chemical functionality such that either non-porous or permanently porous assemblies can be produced. Surface areas and gas uptakes for the latter exceed comparable molecular solids. One of the cages can be converted by recrystallization to produce either porous or non-porous polymorphs with apparent Brunauer–Emmett–Teller surface areas of 550 and 23 m2 g−1, respectively. These results suggest design principles for responsive porous organic solids and for the modular construction of extended materials from prefabricated molecular pores.

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Acknowledgements

We thank the Engineering and Physical Sciences Research Council (EPSRC) for financial support under grant EPSRC/C511794 and Kaneka Corporation, Japan, for financial supporting a research visit for T.T. We thank the STFC for access to Diamond and M.J. Rosseinsky for helpful advice. A.C. is a Royal Society Wolfson Research Merit Award holder.

Author information

Affiliations

  1. Department of Chemistry and Centre for Materials Discovery, University of Liverpool, Crown Street, Liverpool L69 7ZD, UK

    • Tomokazu Tozawa
    • , James T. A. Jones
    • , Shashikala I. Swamy
    • , Shan Jiang
    • , Dave J. Adams
    • , Stephen Shakespeare
    • , Rob Clowes
    • , Darren Bradshaw
    • , Tom Hasell
    • , Samantha Y. Chong
    • , Abbie Trewin
    • , John Bacsa
    • , Alexander Steiner
    •  & Andrew I. Cooper
  2. Corporate Research & Development Division, Kaneka Corporation 5-1-1, Torikai-Nishi, Settsu, Osaka 566-0072, Japan

    • Tomokazu Tozawa
  3. I11 Beamline, Diamond Light Source Limited, Harwell Science and Innovation Campus, Chilton, Didcot OX11 0DE, UK

    • Chiu Tang
    • , Stephen Thompson
    •  & Julia Parker
  4. School of Chemistry, University of St Andrews, North Haugh, St Andrews KY16 9ST, UK

    • Alexandra M. Z. Slawin

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Contributions

T.T., S.I.S., S.J., D.J.A. and S.S. synthesized cages 13, J.T.A.J. and R.C. carried out volumetric sorption measurements, D.B. carried out gravimetric sorption measurements, T.H. carried out microscopy, desolvation studies and TGA, A.T. constructed the molecular models and carried out the sorption simulations, J.B., A.M.Z.S., S.Y.C., C.T., S.T., J.P. and A.S. carried out the crystallography; in particular J.B. and A.S. solved the crucial first structure for the cage 1 ethyl acetate solvate. J.T.A.J. discovered the porous polymorph of 1. A.I.C. conceived the experiments; all authors contributed to writing the paper.

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Correspondence to Andrew I. Cooper.

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DOI

https://doi.org/10.1038/nmat2545

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