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

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. A wide range of porous framework materials has been assembled with a modular approach that takes advantage of prefabricated structural building units (SBUs). Now, it has been shown that functional all-inorganic frameworks can be made from a macrocyclic polyoxometalate SBU — that has a built-in aperture approximately 1 nm in diameter — linked together with redox-switchable metal ions.

Cite this article

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

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