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Triply interlocked covalent organic cages

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.

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Figure 1: Synthesis of interlocked cages 3a–c.
Figure 2: Structures of triply interlocked cages.
Figure 3: Topology of triply interlocked cages.
Figure 4: Matched cage enantiomers interlock more effectively.
Figure 5: Characterization of the monomeric cage, 4a, and catenated cage dimer, 3a.
Figure 6: Matrix-assisted laser desorption/ionization–time of flight (MALDI-TOF) mass spectrum for a mixed cage dimer.

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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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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.

Corresponding author

Correspondence to Andrew I. Cooper.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 2928 kb)

Supplementary information

Crystallographic data for compound 3a (CIF 14 kb)

Supplementary information

Crystallographic data for compound 3b (CIF 75 kb)

Supplementary information

Crystallographic data for compound 3c (CIF 33 kb)

Supplementary information

Crystallographic data for compound 4c with a mesitylene guest (CIF 42 kb)

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Hasell, T., Wu, X., Jones, J. et al. Triply interlocked covalent organic cages. Nature Chem 2, 750–755 (2010). https://doi.org/10.1038/nchem.739

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