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Vernier-Templated Synthesis, Crystal Structure, and Supramolecular Chemistry of a 12-Porphyrin Nanoring

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

Authors

Dmitry V. Kondratuk

Johannes K. Sprafke

Melanie C. O'Sullivan

Luis M.A. Perdigão

Marc Malfois

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JAMES O'SHEA J.OSHEA@NOTTINGHAM.AC.UK
Associate Professor and Reader Inphysics

Amber L. Thompson

Harry L. Anderson



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[BOND]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.

Journal Article Type Article
Publication Date Sep 26, 2014
Journal Chemistry - A European Journal
Print ISSN 0947-6539
Electronic ISSN 1521-3765
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 20
Issue 40
Pages 12826-12834
APA6 Citation Kondratuk, D. V., Sprafke, J. K., O'Sullivan, M. C., Perdigão, L. M., Saywell, A., Malfois, M., …Anderson, H. L. (2014). Vernier-Templated Synthesis, Crystal Structure, and Supramolecular Chemistry of a 12-Porphyrin Nanoring. Chemistry - A European Journal, 20(40), 12826-12834. https://doi.org/10.1002/chem.201403714
DOI https://doi.org/10.1002/chem.201403714
Keywords Conjugation, Macrocycles, Porphyrinoids, Supramolecular chemistry, Template synthesis
Publisher URL http://dx.doi.org/10.1002/chem.201403714
Copyright Statement Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0





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