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Stereochemical plasticity modulates cooperative binding in a CoII12L6 cuboctahedron

Nature Chemistry volume 9, pages 903–908 (2017)Cite this article

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Abstract

Biomolecular receptors are able to process information by responding differentially to combinations of chemical signals. Synthetic receptors that are likewise capable of multi-stimuli response can form the basis of programmable molecular systems, wherein specific input sequences create distinct outputs. Here we report a pseudo-cuboctahedral assembly capable of cooperatively binding anionic and neutral guest species. The binding of pairs of fullerene guests was observed to effect the all-or-nothing cooperative templation of an S6-symmetric host stereoisomer. This bis-fullerene adduct exhibits different cooperativity in binding pairs of anions from the fullerene-free parent: in one case, positive cooperativity is observed, while in another all binding affinities are enhanced by an order of magnitude, and in a third the binding events are only minimally perturbed. This intricate modulation of binding affinity, and thus cooperativity, renders our new cuboctahedral receptor attractive for incorporation into systems with complex, programmable responses to different sets of stimuli.

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Figure 1: Syntheses of the Co12IIL6 isomers 1–3 and their responses to the binding of large anionic guests.
Figure 2: X-ray crystal structure of 1.
Figure 3: Characterization data for 1, (C60)2 ⊂ 2 and (C70)2 ⊂ 2.
Figure 4: Four views of the X-ray crystal structure of (C60)2 ⊂ 2.
Figure 5: The changes observed in the cooperativity parameter (α = 4K2/K1) when fullerenes were present in the cage.
Figure 6: Two views of the X-ray crystal structure of D4-symmetric 3.

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Acknowledgements

This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC). F.J.R. acknowledges Cambridge Australia Scholarships and the Cambridge Trust for PhD funding. We thank Diamond Light Source for time on Beamline I19 (MT11397). We also thank T. Ronson for helpful discussions regarding crystallography, and M. Kieffer and J. Carpenter for assisting with synchrotron X-ray data collections.

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  1. Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, UK

    Felix J. Rizzuto & Jonathan R. Nitschke

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J.R.N. and F.J.R. conceived the study, analysed the results and wrote the manuscript. F.J.R. performed the experiments.

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Correspondence to Jonathan R. Nitschke.

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Supplementary information (PDF 8081 kb)

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Crystallographic data for compound 1 (CIF 11226 kb)

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Crystallographic data for compound 2 hosting two C60 (CIF 51955 kb)

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Crystallographic data for compound 3 (CIF 47585 kb)

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Rizzuto, F., Nitschke, J. Stereochemical plasticity modulates cooperative binding in a CoII12L6 cuboctahedron. Nature Chem 9, 903–908 (2017). https://doi.org/10.1038/nchem.2758

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