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Triply interlocked covalent organic cages

Nature Chemistry volume 2, pages 750755 (2010) | Download Citation

Abstract

Interlocked molecules comprise two or more separate components that are joined by ‘mechanical’ rather than covalent bonds. In other words, these molecular assemblies cannot be dissociated without the cleavage of one or more chemical bonds. Although recent progress has enabled the preparation of such topologies through coordination or templating interactions, three-dimensional interlocked covalent architectures remain difficult to prepare. Here, we present a template-free one-pot synthesis of triply interlocked organic cages. These 20-component dimers consist of two tetrahedral monomeric cages each built from four nodes and six linkers. The monomers exhibit axial chirality, which is recognized by their partner cage during the template-free interlocking assembly process. The dimeric cages also include two well-defined cavities per assembly, which for one of the systems studied led to the formation of a supramolecular host–guest chain. These interlocked organic molecules may prove useful as part of a toolkit for the modular construction of complex porous solids and other supramolecular assemblies.

  • Compound C9H6O3

    Benzene-1,3,5-tricarbaldehyde

  • Compound C3H10N2

    Propane-1,2-diamine

  • Compound C5H12N2

    (1R,2R)-Cyclopentane-1,2-diamine

  • Compound C2H8N2

    Ethane-1,2-diamine

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Acknowledgements

The authors thank the Engineering and Physical Sciences Research Council (EPSRC) for financial support under grants EP/H000925/1 and EP/C511794/1. A.I.C. is a Royal Society Wolfson Research Merit Award holder. A.T. holds a Royal Society University Research Fellowship. We are grateful for the assistance of C. Blythe (HPLC/MS) and S. Higgins (GPC), as well as V. Boote and G. Smith of the Knowledge Centre for Materials Chemistry, University of Manchester (MALDI-TOF) .

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Affiliations

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

    • Tom Hasell
    • , Xiaofeng Wu
    • , James T. A. Jones
    • , John Bacsa
    • , Alexander Steiner
    • , Tamoghna Mitra
    • , Abbie Trewin
    • , Dave J. Adams
    •  & Andrew I. Cooper

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Contributions

A.C., T.H. and D.A. conceived and designed the experiments. The synthetic work was led by T.H. and also involved T.M. and X.W. Characterization and data analysis was carried out by T.H. (FTIR, NMR, TGA), J.J. (NMR, PXRD), J.B. and A.S. (SCXRD). A.S. analysed the number of potential positional isomers for the catenated cages. A.T. was responsible for the modelling work. T.H., A.S. and A.C. led the writing of the paper with input from all co-authors.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Andrew I. Cooper.

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Crystallographic information files

  1. 1.

    Supplementary information

    Crystallographic data for compound 3a

  2. 2.

    Supplementary information

    Crystallographic data for compound 3b

  3. 3.

    Supplementary information

    Crystallographic data for compound 3c

  4. 4.

    Supplementary information

    Crystallographic data for compound 4c with a mesitylene guest

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DOI

https://doi.org/10.1038/nchem.739

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