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Face-directed self-assembly of an electronically active Archimedean polyoxometalate architecture

Nature Chemistry volume 2, pages 308312 (2010) | Download Citation

Abstract

The convergent assembly of metal–organic frameworks has enabled the design of porous materials using a structural building unit approach, but functional systems incorporating pre-assembled structural building unit ‘pore’ openings are rare. Here, we show that the face-directed assembly of a ring-shaped macrocyclic polyoxometalate structural building unit, {P8W48O184}40− with an integrated 1-nm pore as an ‘aperture synthon’, with manganese linkers yields a vast three-dimensional extended framework architecture based on a truncated cuboctahedron. The 1-nm-diameter entrance pores of the {P8W48O184}40− structural building unit lead to approximately spherical 7.24-nm3 cavities containing exchangeable alkali-metal cations that can be replaced by transition-metal ions through a cation exchange process. Control over this process can be exerted by either electrochemically switching the overall framework charge by manipulating the oxidation state of the manganese linker ions, or by physically gating the pores with large organic cations, thus demonstrating how metal–organic framework-like structures with integrated pores and new physical properties can be assembled.

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Acknowledgements

This work was supported by the EPSRC, BP Chemicals, WestCHEM, The Leverhulme Trust and The University of Glasgow. The authors would like to thank M. Beglan for assistance with FP and FAAS analysis and A. Macdonell for the concept movie showing the assembly of the cubic array.

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  1. WestCHEM, Department of Chemistry, The University of Glasgow, University Avenue, Glasgow G12 8QQ, UK

    • Scott G. Mitchell
    • , Carsten Streb
    • , Haralampos N. Miras
    • , Thomas Boyd
    • , De-Liang Long
    •  & Leroy Cronin

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Contributions

S.M. and L.C. designed experiments, analysed data, prepared the figures and wrote the manuscript. C.S. provided invaluable advice and assisted with the PXRD. H.M. performed electrochemistry measurements. D.L. checked the crystallography. T.B. verified the synthesis.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Leroy Cronin.

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DOI

https://doi.org/10.1038/nchem.581

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