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Metal–organic frameworks with dynamic interlocked components

Nature Chemistry volume 4, pages 456–460 (2012)Cite this article

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Abstract

The dynamics of mechanically interlocked molecules such as rotaxanes and catenanes have been studied in solution as examples of rudimentary molecular switches and machines, but in this medium, the molecules are randomly dispersed and their motion incoherent. As a strategy for achieving a higher level of molecular organization, we have constructed a metal–organic framework material using a [2]rotaxane as the organic linker and binuclear Cu(II) units as the nodes. Activation of the as-synthesized material creates a void space inside the rigid framework that allows the soft macrocyclic ring of the [2]rotaxane to rotate rapidly, unimpeded by neighbouring molecular components. Variable-temperature 13C and 2H solid-state NMR experiments are used to characterize the nature and rate of the dynamic processes occurring inside this unique material. These results provide a blueprint for the future creation of solid-state molecular switches and molecular machines based on mechanically interlocked molecules.

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Figure 1: MOF materials are commonly constructed from a combination of rigid linking struts (green) and metal nodes (brown).
Figure 2: Synthesis and X-ray structural characterization of a mechanically interlocked MOF linker.
Figure 3: Structure of UWDM-1 determined by single-crystal X-ray diffraction.
Figure 4: PXRD traces for UWDM-1.
Figure 5: Solid-state 13C and 2H NMR (SSNMR) were used to identify and determine the nature of the dynamic motions occurring inside activated samples of UWDM-1 at various temperatures.

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Acknowledgements

This work was supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada, primarily through Discovery grants to S.J.L. and R.W.S. and partially through a Canada Research Chair programme award to S.J.L. R.W.S. is also grateful for support from NSERC, the Canadian Foundation for Innovation, the Ontario Innovation Trust and the University of Windsor for the development and maintenance of the SSNMR centre. V.N.V. is grateful for financial support provided by the NSERC of Canada through an Alexander Graham Bell Canada Graduate Doctoral Scholarship and by the International Center for Diffraction Data for a Ludo Frevel Crystallography Scholarship. The authors acknowledge M. Revington for technical assistance with solution NMR spectroscopy experiments and S. Zhang for recording electrospray mass spectrometry data.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Windsor, Windsor, N9B 3P4, Ontario, Canada

    V. Nicholas Vukotic, Kristopher J. Harris, Kelong Zhu, Robert W. Schurko & Stephen J. Loeb

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  1. V. Nicholas Vukotic
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  2. Kristopher J. Harris
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  4. Robert W. Schurko
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Contributions

S.J.L. supervised the project. S.J.L. and V.N.V. designed the experiments. V.N.V. performed the synthetic experiments with assistance from K.Z. V.N.V. collected and analysed the PXRD, thermal gravimetric analysis (TGA) and single-crystal X-ray diffraction (SCXRD) data with assistance from S.J.L. K.J.H. collected and analysed the SSNMR data. R.W.S. supervised all SSNMR data collection, analysis and interpretation. S.J.L. wrote the manuscript with significant input from V.N.V., K.J.H., K.Z. and R.W.S.

Corresponding authors

Correspondence to Robert W. Schurko or Stephen J. Loeb.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 2641 kb)

Supplementary information

Crystallographic data for compound 5 (CIF 27 kb)

Supplementary information

Crystallographic data for compound UWDM-1 (CIF 23 kb)

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Vukotic, V., Harris, K., Zhu, K. et al. Metal–organic frameworks with dynamic interlocked components. Nature Chem 4, 456–460 (2012). https://doi.org/10.1038/nchem.1354

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