Article | Published:

Supramolecular nesting of cyclic polymers

Nature Chemistry volume 7, pages 317322 (2015) | Download Citation

Abstract

Advances in template-directed synthesis make it possible to create artificial molecules with protein-like dimensions, directly from simple components. These synthetic macromolecules have a proclivity for self-organization that is reminiscent of biopolymers. Here, we report the synthesis of monodisperse cyclic porphyrin polymers, with diameters of up to 21 nm (750 C–C bonds). The ratio of the intrinsic viscosities for cyclic and linear topologies is 0.72, indicating that these polymers behave as almost ideal flexible chains in solution. When deposited on gold surfaces, the cyclic polymers display a new mode of two-dimensional supramolecular organization, combining encapsulation and nesting; one nanoring adopts a near-circular conformation, thus allowing a second nanoring to be captured within its perimeter, in a tightly folded conformation. Scanning tunnelling microscopy reveals that nesting occurs in combination with stacking when nanorings are deposited under vacuum, whereas when they are deposited directly from solution under ambient conditions there is stacking or nesting, but not a combination of both.

  • Compound C716H898N40O40Si2Zn10

    Silicon-protected linear porphyrin decamer

  • Compound C680H822N40O40Zn10

    Linear porphyrin decamer

  • Compound C72H48N6

    4,4'-(3',4',5',6'-tetrakis(4-(pyridin-4-yl)phenyl)-[1,1':2',1''-terphenyl]-4,4''-diyl)dipyridine

  • Compound C156H134N12O8

    2,3,7,8,12,13,17,18-octakis(3-butoxy-4-(pyridin-4-ylethynyl)phenyl)porphyrin

  • Compound C680H820N40O40Zn10

    Cyclic porphyrin decamer

  • Compound C1360H1640N80O80Zn20

    Cyclic porphyrin icosamer

  • Compound C2040H2460N120O120Zn30

    Cyclic porphyrin triacontamer

  • Compound C2720H3280N160O160Zn40

    Cyclic porphyrin tetracontamer

  • Compound C3400H4100N200O200Zn50

    Cyclic porphyrin pentacontamer

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Acknowledgements

The authors thank the Engineering and Physical Sciences Research Council (EPSRC), the European Research Council (ERC) and the Clarendon Fund for support, and the EPSRC mass spectrometry service (Swansea) for mass spectra.

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Affiliations

  1. Department of Chemistry, Oxford University, Oxford OX1 3TA, UK

    • Dmitry V. Kondratuk
    •  & Harry L. Anderson
  2. Department of Physics & Astronomy, University of Nottingham, Nottingham NG7 2RD, UK

    • Luís M. A. Perdigão
    • , Ayad M. S. Esmail
    • , James N. O'Shea
    •  & Peter H. Beton

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Contributions

H.L.A. and D.V.K. designed the synthesis of cyclic polymers. P.H.B., L.M.A.P., J.N.O.S. and A.M.S.E. developed the protocols required for STM imaging. Synthesis and solution-phase characterization were carried out by D.V.K. UHV and ambient STM experiments were carried out by L.M.A.P. and A.M.S.E., respectively. The manuscript was written by D.V.K., H.L.A. and P.H.B. All authors contributed to data analysis and edited the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Peter H. Beton or Harry L. Anderson.

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https://doi.org/10.1038/nchem.2182

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