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Trapping virtual pores by crystal retro-engineering

Nature Chemistry volume 7, pages 153–159 (2015)Cite this article

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Abstract

Stable guest-free porous molecular crystals are uncommon. By contrast, organic molecular crystals with guest-occupied cavities are frequently observed, but these cavities tend to be unstable and collapse on removal of the guests—this feature has been referred to as ‘virtual porosity’. Here, we show how we have trapped the virtual porosity in an unstable low-density organic molecular crystal by introducing a second molecule that matches the size and shape of the unstable voids. We call this strategy ‘retro-engineering’ because it parallels organic retrosynthetic analysis, and it allows the metastable two-dimensional hexagonal pore structure in an organic solvate to be trapped in a binary cocrystal. Unlike the crystal with virtual porosity, the cocrystal material remains single crystalline and porous after removal of guests by heating.

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Figure 1: Synthesis of ‘porous organic cage’ molecules.
Figure 2: A metastable solvate phase of a porous cage, phase 1, has virtual 2D pores but this transforms over time to a denser phase, CC3α, with 3D pores.
Figure 3: Retro-engineering a binary porous cocrystal.
Figure 4: 2D porosity in the stable binary cocrystal is retro-engineered from the unstable CC3 solvate.

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Acknowledgements

The authors gratefully acknowledge the Engineering and Physical Sciences Research Council (EP/H000925/1) and European Research Council (ERC) under the European Union's Seventh Framework Programme/ERC Grant Agreement No. [321156] for financial support. K.E.J. is a Royal Society University Research Fellow. We thank R. Clowes for assistance with the sorption measurements and S. Higgins for assistance with the robotic handling apparatus. The authors thank Diamond Light Source for access to beamlines I19 (MT8728) and I11 (EE9282) that contributed to the results presented here and also M. R. Warren and S. A. Barnett for their assistance during the single-crystal gas cell studies.

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Authors and Affiliations

  1. Department of Chemistry and Centre for Materials Discovery, University of Liverpool, L69 3BX, UK

    Marc A. Little, Michael E. Briggs, James T. A. Jones, Marc Schmidtmann, Tom Hasell, Samantha Y. Chong, Linjiang Chen & Andrew I. Cooper

  2. Department of Chemistry, Imperial College London, SW7 2AZ, UK

    Kim E. Jelfs

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Contributions

A.I.C. conceived the project. M.E.B., M.A.L. and T.H. prepared the cage molecules. M.A.L., T.H. and J.T.A.J. crystallized and cocrystallized the cage molecules. M.A.L., M.S. and S.Y.C. interpreted the crystal data. M.A.L., T.H. and L.C. interpreted the sorption data. K.E.J. modelled the cage conformers. All authors interpreted the structures and contributed to the preparation of the manuscript.

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Correspondence to Andrew I. Cooper.

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Supplementary information

Supplementary information

Supplementary information (PDF 14892 kb)

Supplementary information

Crystallographic data for [3+2]#1.(H2O)13. (CIF 3185 kb)

Supplementary information

Crystallographic data for [3+2]#5. (CIF 2394 kb)

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Crystallographic data for 2(CC3-R)([3+2]#5) at 400K. (CIF 2363 kb)

Supplementary information

Crystallographic data for 2(CC3-R)([3+2]#5) at 450K. (CIF 2334 kb)

Supplementary information

Crystallographic data for (CC3-R)2.[3+2]#5 at 100K. (CIF 2632 kb)

Supplementary information

Crystallographic data for (CC3-R)2.[3+2]#5 at 300K. (CIF 2559 kb)

Supplementary information

Crystallographic data for (CC3-R)2.[3+2]#5 under dynamic vacuum. (CIF 1427 kb)

Supplementary information

Crystallographic data for (CC3-R)2.[3+2]#5.(CHCl3)2.(MeOH)8 at 100K. (CIF 2765 kb)

Supplementary information

Crystallographic data for (CC3-R)2.[3+2]#5.(CHCl3)0.5.(MeOH)1.5 at 300K. (CIF 2744 kb)

Supplementary information

Crystallographic data for CC3-R.CH2Cl2.(MeOH)7.(H2O)2.5. (CIF 3369 kb)

Supplementary information

Crystallographic data for CC3-R.(MeOH)11.(H2O)4. (CIF 2412 kb)

Supplementary information

Crystallographic data for (CC3-R)2. (CIF 1648 kb)

Supplementary information

Crystallographic data for (CC3-R)2.(CH2Cl2)0.5.(MeOH)11.(H2O)10.5. (CIF 5903 kb)

Supplementary information

Crystallographic data for (CC3-R)2.(CHCl3)3.(MeOH)7.(H2O)4.75. (CIF 4810 kb)

Supplementary information

Crystallographic data for Reduced [3+2]#4.(H2O)15. (CIF 2725 kb)

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Little, M., Briggs, M., Jones, J. et al. Trapping virtual pores by crystal retro-engineering. Nature Chem 7, 153–159 (2015). https://doi.org/10.1038/nchem.2156

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