Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Molecular shape sorting using molecular organic cages

Nature Chemistry volume 5, pages 276–281 (2013)Cite this article

Subjects

Abstract

The energy-efficient separation of chemical feedstocks is a major sustainability challenge. Porous extended frameworks such as zeolites or metal–organic frameworks are one potential solution to this problem. Here, we show that organic molecules, rather than frameworks, can separate other organic molecules by size and shape. A molecular organic cage is shown to separate a common aromatic feedstock (mesitylene) from its structural isomer (4-ethyltoluene) with an unprecedented perfect specificity for the latter. This specificity stems from the structure of the intrinsically porous cage molecule, which is itself synthesized from a derivative of mesitylene. In other words, crystalline organic molecules are used to separate other organic molecules. The specificity is defined by the cage structure alone, so this solid-state ‘shape sorting’ is, uniquely, mirrored for cage molecules in solution. The behaviour can be understood from a combination of atomistic simulations for individual cage molecules and solid-state molecular dynamics simulations.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Molecules to separate molecules.
Figure 2: Synthesis of organic cages.
Figure 3: Solid-state shape selectivity can be understood in terms of the structure and dynamics of discrete, isolated cage molecules.
Figure 4: The diamondoid pore network for crystalline CC3 carries the steric signature of the discrete cage building units.
Figure 5: Solid-state shape selectivity and chromatographic separations using crystalline porous organic cages.
Figure 6: Solid-state molecular simulations reveal diffusion mechanisms for the organic guests.

Similar content being viewed by others

References

  1. Bloch, E. D. et al. Hydrocarbon separations in a metal–organic framework with open iron(II) coordination sites. Science 335, 1606–1610 (2012).

    Article  CAS  Google Scholar 

  2. Alaerts, L. et al. Selective adsorption and separation of ortho-substituted alkylaromatics with the microporous aluminum terephthalate MIL-53. J. Am. Chem. Soc. 130, 14170–14178 (2008).

    Article  CAS  Google Scholar 

  3. Alaerts, L. et al. Selective adsorption and separation of xylene isomers and ethylbenzene with the microporous vanadium(IV) terephthalate MIL-47. Angew. Chem. Int. Ed. 46, 4293–4297 (2007).

    Article  CAS  Google Scholar 

  4. Alaerts, L., Maes, M., van der Veen, M. A., Jacobs, P. A. & De Vos, D. E. Metal–organic frameworks as high-potential adsorbents for liquid-phase separations of olefins, aklylnaphthalenes and dichlorobenzenes. Phys. Chem. Chem. Phys. 11, 2903–2911 (2009).

    Article  CAS  Google Scholar 

  5. Maes, M. et al. Separation of C5-hydrocarbons on microporous materials: complementary performance of MOFs and zeolites. J. Am. Chem. Soc. 132, 2284–2292 (2010).

    Article  CAS  Google Scholar 

  6. Vaidhyanathan, R. et al. A family of nanoporous materials based on an amino acid backbone. Angew. Chem. Int. Ed. 45, 6495–6499 (2006).

    Article  CAS  Google Scholar 

  7. Nuzhdin, A. L., Dybtsev, D. N., Bryliakov, K. P., Talsi, E. P. & Fedin, V. P. Enantioselective chromatographic resolution and one-pot synthesis of enantiomerically pure sulfoxides over a homochiral Zn–organic framework. J. Am. Chem. Soc. 129, 12958–12959 (2007).

    Article  CAS  Google Scholar 

  8. Kulprathipanja, S. & James, R. B. in Zeolites in Industrial Separation and Catalysis (ed. Kulprathipanja, S.) 173–202 (Wiley-VCH, 2010).

    Book  Google Scholar 

  9. Li, J-R., Sculley, J. & Zhou, H. C. Metal–organic frameworks for separations. Chem. Rev. 112, 869–932 (2011).

    Article  Google Scholar 

  10. Pedersen, C. J. The discovery of crown ethers. Angew. Chem. Int. Ed. Engl. 27, 1021–1027 (1988).

    Article  Google Scholar 

  11. Tashiro, S., Kubota, R. & Shionoya, M. Metal–macrocycle framework (MMF): supramolecular nano-channel surfaces with shape sorting capability. J. Am. Chem. Soc. 134, 2461–2464 (2011).

    Article  Google Scholar 

  12. Mastalerz, M. Shape-persistent organic cage compounds by dynamic covalent bond formation. Angew. Chem. Int. Ed. 49, 5042–5053 (2010).

    Article  CAS  Google Scholar 

  13. Dube, H. & Rebek, J. Selective guest exchange in encapsulation complexes using light of different wavelengths. Angew. Chem. Int. Ed. 51, 3207–3210 (2012).

    Article  CAS  Google Scholar 

  14. Tozawa, T. et al. Porous organic cages. Nature Mater. 8, 973–978 (2009).

    Article  CAS  Google Scholar 

  15. Hasell, T. et al. Triply interlocked covalent organic cages. Nature Chem. 2, 750–755 (2010).

    Article  CAS  Google Scholar 

  16. Ro, S., Rowan, S. J., Pease, A. R., Cram, D. J. & Stoddart, J. F. Dynamic hemicarcerands and hemicarceplexes Org. Lett. 2, 2411–2414 (2000).

  17. Hasell, T., Schmidtmann, M., Stone, C. A., Smith, M. W. & Cooper, A. I. Reversible water uptake by a stable imine-based porous organic cage. Chem. Commun. 48, 4689–4691 (2012).

    Article  CAS  Google Scholar 

  18. Jones, J. T. A. et al. Modular and predictable assembly of porous organic molecular crystals. Nature 474, 367–371 (2011).

    Article  CAS  Google Scholar 

  19. Smith, W., Yong, C. W. & Rodger, P. W. DL_POLY: application to molecular simulation. Mol. Simul. 28, 385–471 (2002).

    Article  CAS  Google Scholar 

  20. Brutschy, M., Schneider, M. W., Mastalerz, M. & Waldvogel, S. R. Porous organic cage compounds as highly potent affinity materials for sensing by quartz crystal microbalances. Adv. Mater. 24, 6049–6052 (2012).

    Article  CAS  Google Scholar 

  21. Lydon, D. P., Campbell, N. L., Adams, D. J. & Cooper, A. I. Scalable synthesis for porous organic cages. Synth. Commun. 41, 2146–2151 (2011).

    Article  CAS  Google Scholar 

  22. Mastalerz, M., Schneider, M. W., Oppel, I. M. & Presly, O. A salicylbisimine cage compound with high surface area and selective CO2/CH4 adsorption. Angew. Chem. Int. Ed. 50, 1046–1051 (2010).

    Article  Google Scholar 

  23. Hasell, T., Chong, S. Y., Jelfs, K. E., Adams, D. J. & Cooper, A. I. Porous organic cage nanocrystals by solution mixing. J. Am. Chem. Soc. 134, 588–598 (2012).

    Article  CAS  Google Scholar 

  24. Bushell, A. F. et al. Nanoporous organic polymer/cage composite membranes, Angew. Chem. Int. Ed. doi: http:dx.doi.org/10.1002/anie.20120633910.1002/anie.201206339 (2012).

  25. Holden, D. et al. Bespoke force field for simulating the molecular dynamics of porous organic cages. J. Phys. Chem. C 116, 16639–16651 (2012).

    Article  CAS  Google Scholar 

  26. Hoover, W. G. Canonical dynamics – equilibrium phase-space distributions. Phys. Rev. A 31, 1695–1697 (1985).

    Article  CAS  Google Scholar 

  27. Forester, T. R. & Smith, W. SHAKE, rattle, and roll: efficient constraint algorithms for linked rigid bodies. J. Comput. Chem. 19, 102–111 (1998).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge funding from the EPSRC (EP/H000925/1) and the Leverhulme Trust (F/00025/Al). A.C. is a Royal Society Wolfson award holder. The authors thank J.T.A. Jones for assistance with NMR measurements.

Author information

Authors and Affiliations

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

    Tamoghna Mitra, Kim E. Jelfs, Marc Schmidtmann, Adham Ahmed, Samantha Y. Chong, Dave J. Adams & Andrew I. Cooper

Authors
  1. Tamoghna Mitra
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kim E. Jelfs
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Marc Schmidtmann
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Adham Ahmed
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Samantha Y. Chong
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Dave J. Adams
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Andrew I. Cooper
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

A.C. conceived the project. T.M., D.A. and A.C. designed the experiments. T.M. prepared the cages and carried out the sorption experiments. K.J. conceived the modelling strategy and performed the molecular simulations. M.S. solved the single-crystal structures and S.C. refined the powder X-ray diffraction data. T.M. and A.A. performed the breakthrough experiments.

Corresponding author

Correspondence to Andrew I. Cooper.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 2052 kb)

Supplementary information

Supplementary movie 1 (WMV 4433 kb)

Supplementary information

Supplementary movie 2 (MOV 12923 kb)

Supplementary information

Supplementary movie 3 (MOV 24790 kb)

Supplementary information

Supplementary movie 4 (MOV 6705 kb)

Supplementary information

Crystallographic data for the complex between mesitylene and compound CC3 (CIF 56 kb)

Supplementary information

Crystallographic data for the complex between meta-xylene and compound CC3 (CIF 88 kb)

Supplementary information

Crystallographic data for the complex between para-xylene and compound CC3 at 100K (CIF 42 kb)

Supplementary information

Crystallographic data for the complex between para-xylene and compound CC3 at 295K (CIF 41 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Mitra, T., Jelfs, K., Schmidtmann, M. et al. Molecular shape sorting using molecular organic cages. Nature Chem 5, 276–281 (2013). https://doi.org/10.1038/nchem.1550

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.1550

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing