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


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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Figure 1: Open framework material 1 is built from the face-directed assembly of a highly anionic {P8W48O184}40− molecular building unit, which incorporates a 1-nm pore, combined with electrophilic manganese linkers, which are redox-switchable.
Figure 2: Face-directed assembly of six {P8W48O184}40− heteropolyanions through multiple {Mn–O–W} bonds along all axes, giving rise to a geometrically well-defined Archimedean solid: the truncated cuboctahedron.
Figure 3: UV spectrophotometric exchange experiments were used to establish the cation exchange capabilities of the solvent-accessible voids of 1 over a 24-h period.


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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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Authors and Affiliations



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.

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Correspondence to Leroy Cronin.

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Mitchell, S., Streb, C., Miras, H. et al. Face-directed self-assembly of an electronically active Archimedean polyoxometalate architecture. Nature Chem 2, 308–312 (2010).

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