Vernier templating and synthesis of a 12-porphyrin nano-ring

Abstract

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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Figure 1: Vernier templating.
Figure 2: Synthesis and NMR characterization of the 12-porphyrin nano-ring.
Figure 3: Characterization of the 12-porphyrin nano-ring by SAXS and STM.
Figure 4: Classical template-directed synthesis of nano-ring c -P12.

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Acknowledgements

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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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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Correspondence to Harry L. Anderson.

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The authors declare no competing financial interests.

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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. (PDF 4474 kb)

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O’Sullivan, M., Sprafke, J., Kondratuk, D. et al. Vernier templating and synthesis of a 12-porphyrin nano-ring. Nature 469, 72–75 (2011). https://doi.org/10.1038/nature09683

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