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An M18L24 stellated cuboctahedron through post-stellation of an M12L24 core

Nature Chemistry volume 4, pages 330–333 (2012)Cite this article

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Abstract

Platonic and Archimedean polyhedra, well-known to mathematicians, have been recently constructed by chemists at a molecular scale by defining the vertices and the edges with metal ions (M) and organic ligands (L), respectively. Here, we report the first synthesis of a concave-surface ‘stellated polyhedron’, constructed by extending the faces of its precursor polyhedron until they intersect, forming additional nodes. Our approach involves the formation of an M12L24 cuboctahedron core, the linkers of which each bear a pendant ligand site that is subsequently able to bind an additional metal centre to form the stellated M18L24 cuboctahedron. During this post-stellation process, the square faces of the M12L24 core are closed by coordination of the pendant moieties to the additional metal centres, but they are re-opened on removing these metals ions from the vertices. This behaviour is reminiscent of the analogous metal-triggered gate opening–closing switches found in spherical virus capsids.

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Figure 1: Cartoons of a cuboctahedron (left) and its stellated counterpart (right).
Figure 2: Synthesis and structural analyses of cuboctahedron 2.
Figure 3: Crystal structure of 2 (PF6− salt) looking down through a triangular window (left) and a square window (right).
Figure 4: Reversible conversion between an M12L24 cuboctahedron (2) and an M18L24 stellated cuboctahedron (3) through gate opening–closing.
Figure 5: Crystal structure of 4 looking down through a triangular window (left) and a stellated vertex (right).

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Acknowledgements

This research was supported by the CREST project of the Japan Science and Technology Agency (JST), for which M.F. is the principal investigator, and also in part by KAKENHI, MEXT. Synchrotron X-ray diffraction studies were performed at KEK and SPring-8. The authors thank T. Ozeki for valuable suggestions on the refinements of the X-ray structures.

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Authors and Affiliations

  1. Department of Applied Chemistry, School of Engineering, The University of Tokyo, and Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Corporation (JST), 7-3-1 Hongo, Tokyo, 113-8656, Bunkyo-ku, Japan

    Qing-Fu Sun, Sota Sato & Makoto Fujita

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  1. Qing-Fu Sun
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Contributions

M.F. and Q.-F.S. conceived and designed the experiments and wrote the manuscript. Q.-F.S. performed the experiments and analysed the data. S.S. contributed the diffraction and NMR studies and participated in discussions throughout.

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Correspondence to Makoto Fujita.

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Sun, QF., Sato, S. & Fujita, M. An M18L24 stellated cuboctahedron through post-stellation of an M12L24 core. Nature Chem 4, 330–333 (2012). https://doi.org/10.1038/nchem.1285

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