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A Star of David catenane

Nature Chemistry volume 6, pages 978–982 (2014)Cite this article

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Abstract

We describe the synthesis of a [2]catenane that consists of two triply entwined 114-membered rings, a molecular link. The woven scaffold is a hexameric circular helicate generated by the assembly of six tris(bipyridine) ligands with six iron(II) cations, with the size of the helicate promoted by the use of sulfate counterions. The structure of the ligand extension directs subsequent covalent capture of the catenane by ring-closing olefin metathesis. Confirmation of the Star of David topology (two rings, six crossings) is provided by NMR spectroscopy, mass spectrometry and X-ray crystallography. Extraction of the iron(II) ions with tetrasodium ethylenediaminetetraacetate affords the wholly organic molecular link. The self-assembly of interwoven circular frameworks of controlled size, and their subsequent closure by multiple directed covalent bond-forming reactions, provides a powerful strategy for the synthesis of molecular topologies of ever-increasing complexity.

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Figure 1: Assembly of a hexameric circular iron(II) helicate [2](PF6)12 and subsequent ring closure to form a Star of David [2]catenate, [4](PF6)12.
Figure 2: 1H NMR spectra (600 MHz, 298 K, CD3CN/CDCl3 (1:1) (a–d), CDCl3 (e)) of uncoordinated ligand strand 1, linear (3) and circular (2) helicates, and metallated (4) and demetallated (5) Star of David [2]catenanes.
Figure 3: X-ray crystal structure of Star of David catenane, [4](PF6)(Ph4B)11.
Figure 4: Demetallation of the Star of David [2]catenate to form the wholly organic Star of David [2]catenand 5 and the unlinked macrocycle 6.

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Acknowledgements

This work was supported by the Engineering and Physical Sciences Research Council (EPSRC). The authors thank the Diamond Light Source (UK), R. E. P. Winpenny and G. Whitehead (University of Manchester) for synchrotron beamtime on I19 (XR029), the EPSRC National Mass Spectrometry Service Centre (Swansea, UK) for data collection, and J-F. Lemonnier and M. Wilson (University of Manchester) for useful discussions and illustrations.

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  1. School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK

    David A. Leigh, Robin G. Pritchard & Alexander J. Stephens

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  1. David A. Leigh
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  2. Robin G. Pritchard
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  3. Alexander J. Stephens
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Contributions

A.J.S. carried out the synthesis and characterization studies, helped plan the experiments and write the manuscript. R.G.P. solved the crystal structure. D.A.L. helped plan the experiments and write the manuscript.

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Correspondence to David A. Leigh.

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The authors declare no competing financial interests.

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Crystallographic data for compound 4 (CIF 167 kb)

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Leigh, D., Pritchard, R. & Stephens, A. A Star of David catenane. Nature Chem 6, 978–982 (2014). https://doi.org/10.1038/nchem.2056

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