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Cascading transformations within a dynamic self-assembled system

Nature Chemistry volume 2, pages 684–687 (2010)Cite this article

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Abstract

Molecular subcomponents such as phosphate groups are often passed between biomolecules during complex signalling cascades, the flow of which define the motion of the machinery of life. Here, we show how an abiological system consisting of organic subcomponents knitted together by metal-ion coordination can respond to simple signals in complex ways. A CuI3 helicate transformed into its ZnII2CuI analogue following the addition of zinc(II), and the ejected copper(I) went on to induce the self-assembly of a CuI2 helicate from other free subcomponents present in solution. The addition of an additional subcomponent, 8-aminoquinoline, resulted in the formation of a third, more stable CuI3 helicate, requiring the destruction of both the ZnII2CuI and CuI2 helicates to scavenge sufficient CuI for the new structure. This system thus demonstrates two examples in which the application of one signal provokes two distinct responses involving the creation or destruction of complex assemblies as the system seeks thermodynamic equilibrium following perturbation.

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Figure 1: Schematic of the transformations in a dynamic self-assembled system.
Figure 2: Syntheses of homometallic double helicate 1 and heterometallic double helicate 2.
Figure 3: Crystal structures of 1 and 2: C, grey; N, lilac; O, red: Cu, yellow: Zn, blue.
Figure 4: Self-assembling system in which the addition of one signal (ZnII or 8-aminoquinoline) induced two distinct transformations.
Figure 5: 1H NMR spectra of the three states of the complex self-assembling system shown in Fig. 4.

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Acknowledgements

This work was funded by an ERA-chemistry collaborative grant. J.R.N. acknowledges financial support from the Walters-Kundert Charitable Trust, the US Army Research Office and Marie Curie Intra-European Fellowship Scheme of the 7th European Framework Program (XdH). Mass spectra were provided by the UK Engineering and Physical Sciences Research Council National MS Service Centre at Swansea.

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Authors and Affiliations

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

    Victoria E. Campbell, Xavier de Hatten & Jonathan R. Nitschke

  2. Institut Européen de Chimie et Biologie, Université de Bordeaux-CNRS UMR5248 and UMS3033, 2 rue Robert Escarpit, Pessac, 33607, France

    Xavier de Hatten, Nicolas Delsuc, Brice Kauffmann & Ivan Huc

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  1. Victoria E. Campbell
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Contributions

J.R.N. conceived the study. V.E.C., J.R.N. and I.H. designed and debugged the experiments. N.D. and X.H. synthesized compound A. V.E.C. synthesized and characterized compounds 1 and 2. V.E.C. and N.D. obtained X-ray quality crystals of 1 and 2. B.K. and I.H. analysed the crystallographic data. V.E.C., J.R.N. and I.H. wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Ivan Huc or Jonathan R. Nitschke.

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Supplementary information

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Crystallographic data for helicate 1 (CIF 60 kb)

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Crystallographic data for helicate 2 (CIF 140 kb)

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Campbell, V., de Hatten, X., Delsuc, N. et al. Cascading transformations within a dynamic self-assembled system. Nature Chem 2, 684–687 (2010). https://doi.org/10.1038/nchem.693

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