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

Kondratuk, Dmitry V. and Sprafke, Johannes K. and O'Sullivan, Melanie C. and Perdigão, Luis M.A. and Saywell, Alexander and Malfois, Marc and O'Shea, James N. and Beton, Peter H. and Thompson, Amber L. and Anderson, Harry L. (2014) Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-Porphyrin nanoring. Chemistry - a European Journal, 20 . pp. 12826-12834. ISSN 1521-3765

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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.

Item Type: Article
Keywords: Conjugation, Macrocycles, Porphyrinoids, Supramolecular chemistry, Template synthesis
Schools/Departments: University of Nottingham UK Campus > Faculty of Science > School of Physics and Astronomy
Identification Number: https://doi.org/10.1002/chem.201403714
Depositing User: O'Shea, Dr James N
Date Deposited: 14 Jul 2016 10:29
Last Modified: 17 Sep 2016 18:26
URI: http://eprints.nottingham.ac.uk/id/eprint/34935

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