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Kondratuk DV, Sprafke JK, O'Sullivan MC, et al. Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-porphyrin nanoring. Chemistry. 2014;20(40):12826-34doi: 10.1002/chem.201403714.
Kondratuk, D. V., Sprafke, J. K., O'Sullivan, M. C., Perdigao, L. M., Saywell, A., Malfois, M., O'Shea, J. N., Beton, P. H., Thompson, A. L., & Anderson, H. L. (2014). Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-porphyrin nanoring. Chemistry (Weinheim an der Bergstrasse, Germany), 20(40), 12826-34. https://doi.org/10.1002/chem.201403714
Kondratuk, Dmitry V, et al. "Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-porphyrin nanoring." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 20,40 (2014): 12826-34. doi: https://doi.org/10.1002/chem.201403714
Kondratuk DV, Sprafke JK, O'Sullivan MC, Perdigao LM, Saywell A, Malfois M, O'Shea JN, Beton PH, Thompson AL, Anderson HL. Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-porphyrin nanoring. Chemistry. 2014 Sep 26;20(40):12826-34. doi: 10.1002/chem.201403714. Epub 2014 Aug 25. PMID: 25154736; PMCID: PMC4517159.
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Chemistry. 2014 Sep 26;20(40):12826-34. doi: 10.1002/chem.201403714. Epub 2014 Aug 25.

Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-porphyrin nanoring.

Chemistry (Weinheim an der Bergstrasse, Germany)

Dmitry V Kondratuk, Johannes K Sprafke, Melanie C O'Sullivan, Luis M A Perdigao, Alex Saywell, Marc Malfois, James N O'Shea, Peter H Beton, Amber L Thompson, Harry L Anderson

Affiliations

  1. Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford, OX1 3TA (UK).

PMID: 25154736 PMCID: PMC4517159 DOI: 10.1002/chem.201403714

Abstract

Vernier templating exploits a mismatch between the number of binding sites in a template and a reactant to direct the formation of a product that is large enough to bind several template units. Here, we present a detailed study of the Vernier-templated synthesis of a 12-porphyrin nanoring. NMR and small-angle X-ray scattering (SAXS) analyses show that Vernier complexes are formed as intermediates in the cyclo-oligomerization reaction. UV/Vis/NIR titrations show that the three-component assembly of the 12-porphyrin nanoring figure-of-eight template complex displays high allosteric cooperativity and chelate cooperativity. This nanoring-template 1:2 complex is among the largest synthetic molecules to have been characterized by single-crystal analysis. It crystallizes as a racemate, with an angle of 27° between the planes of the two template units. The crystal structure reveals many unexpected intramolecular C-H⋅⋅⋅N contacts involving the tert-butyl side chains. Scanning tunneling microscopy (STM) experiments show that molecules of the 12-porphyrin template complex can remain intact on the gold surface, although the majority of the material unfolds into the free nanoring during electrospray deposition.

© 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Keywords: conjugation; macrocycles; porphyrinoids; supramolecular chemistry; template synthesis

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