Templates are widely used to arrange molecular components so they can be covalently linked into complex molecules that are not readily accessible by classical synthetic methods1,2,3,4,5,6,7. Nature uses sophisticated templates such as the ribosome, whereas chemists use simple ions or small molecules. But as we tackle the synthesis of larger targets, we require larger templates—which themselves become synthetically challenging. Here we show that Vernier complexes can solve this problem: if the number of binding sites on the template, nT, is not a multiple of the number of binding sites on the molecular building blocks, nB, then small templates can direct the assembly of relatively large Vernier complexes where the number of binding sites in the product, nP, is the lowest common multiple of nB and nT (refs 8, 9). We illustrate the value of this concept for the covalent synthesis of challenging targets by using a simple six-site template to direct the synthesis of a 12-porphyrin nano-ring with a diameter of 4.7 nm, thus establishing Vernier templating as a powerful new strategy for the synthesis of large monodisperse macromolecules.

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  1. 1.

    eds. Templated Organic Synthesis (VCH-Wiley, 1999)

  2. 2.

    , & Expanding roles for templates in synthesis. Acc. Chem. Res. 26, 469–475 (1993)

  3. 3.

    et al. Molecular Borromean rings. Science 304, 1308–1312 (2004)

  4. 4.

    et al. An unusual nickel-copper-mediated alkyne homocoupling reaction for the active-template synthesis of [2]rotaxanes. J. Am. Chem. Soc. 132, 6243–6248 (2010)

  5. 5.

    et al. A conjugated polycarbazole ring around a porphyrin. Angew. Chem. Int. Ed. 45, 4685–4690 (2006)

  6. 6.

    et al. Enhanced π-conjugation around a porphyrin[6] nanoring. Angew. Chem. Int. Ed. 47, 4993–4996 (2008)

  7. 7.

    , , & Template-directed synthesis of a π-conjugated porphyrin nanoring. Angew. Chem. Int. Ed. 46, 3122–3125 (2007)

  8. 8.

    , , & A molecular vernier. Tetrahedr. Lett. 39, 3675–3678 (1998)

  9. 9.

    & Accurate length control of supramolecular oligomerization: Vernier assemblies. J. Am. Chem. Soc. 128, 8975–8979 (2006)

  10. 10.

    Self-assembly in synthetic routes to molecular devices. Biological principles and chemical perspectives: a review. N. J. Chem. 15, 153–180 (1991)

  11. 11.

    et al. Intramolecular energy transfer within butadiyne-linked chlorophyll and porphyrin dimer-faced, self-assembled prisms. J. Am. Chem. Soc. 130, 4277–4284 (2008)

  12. 12.

    et al. Conformation and packing of porphyrin polymer chains deposited using electrospray on a gold surface. Angew. Chem. Int. Ed. 49, 9136–9139 (2010)

  13. 13.

    & A giant conjugated molecular ring. Angew. Chem. Int. Ed. 42, 3176–3179 (2003)

  14. 14.

    , & Schalley, C. A. & Bäuerle, P. Giant cyclo[n]thiophenes with extended π-conjugation. Angew. Chem. Int. Ed. 48, 6632–6635 (2009)

  15. 15.

    et al. Giant macrocycles composed of thiophene, acetylene, and ethylene building blocks. J. Am. Chem. Soc. 128, 16740–16747 (2006)

  16. 16.

    et al. Persistent currents in normal metal rings. Science 326, 272–275 (2009)

  17. 17.

    et al. Crystal structure of an integral membrane light-harvesting complex from photosynthetic bacteria. Nature 374, 517–521 (1995)

  18. 18.

    et al. Crystal structure of the RC-LH1 core complex from Rhodopseudomonas palustris. Science 302, 1969–1972 (2003)

  19. 19.

    , & Cyclic porphyrin arrays as artificial photosynthetic antenna: synthesis and excitation energy transfer. Chem. Soc. Rev. 36, 831–845 (2007)

  20. 20.

    et al. Assemblies of supramolecular porphyrin dimers in pentagonal and hexagonal arrays exhibiting light-harvesting antenna function. J. Am. Chem. Soc. 128, 4612–4623 (2006)

  21. 21.

    , , & Dynamics of excited-state conformational relaxation and electronic delocalization in conjugated porphyrin oligomers. J. Am. Chem. Soc. 130, 10171–10178 (2008)

  22. 22.

    & Cooperative self-assembly of double-strand conjugated porphyrin ladders. J. Am. Chem. Soc. 121, 11538–11545 (1999)

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We thank the Engineering and Physical Sciences Research Council (EPSRC), the Diamond Light Source, the European Commission (EU-contract: MRTN-CT-2006-036040, THREADMILL) and the Clarendon Fund for support; the EPSRC mass spectrometry service (Swansea) for mass spectra; and B. Odell for help with NMR spectroscopy.

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    • Melanie C. O’Sullivan
    •  & Johannes K. Sprafke

    These authors contributed equally to this work.


  1. Department of Chemistry, Oxford University, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA, UK

    • Melanie C. O’Sullivan
    • , Johannes K. Sprafke
    • , Dmitry V. Kondratuk
    • , Corentin Rinfray
    • , Timothy D. W. Claridge
    •  & Harry L. Anderson
  2. School of Physics & Astronomy, University of Nottingham, Nottingham, NG7 2RD, UK

    • Alex Saywell
    • , Matthew O. Blunt
    • , James N. O’Shea
    •  & Peter H. Beton
  3. Diamond Light Source Ltd, Harwell Science and Innovation Campus, Didcot OX11 0DE, UK

    • Marc Malfois


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H.L.A. designed the project and wrote the manuscript. J.K.S., M.C.O., D.K. and C.R. carried out most of the experimental work. T.D.W.C. provided expertise with NMR analysis. STM was performed by A.S. and M.O.B., supervised by J.N.O. and P.H.B. SAXS analysis was performed by J.K.S. and H.L.A. with help from M.M. All authors edited the manuscript.

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The authors declare no competing financial interests.

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Correspondence to Harry L. Anderson.

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    The file contains Supplementary Information Sections A-D (see Contents List for details). It also includes Supplementary Figures 1-40 with legends and Supplementary References.

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