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

DOI: 10.1002/chem.201403714 DOI Help
PMID: 25154736 PMID Help

Authors: Dmitry V. Kondratuk (University of Oxford) , Johannes K. Sprafke (University of Oxford) , Melanie C. O'sullivan (University of Oxford) , Luis M. A. Perdigao (University of Nottingham) , Alex Saywell (University of Nottingham) , Marc Malfois (Diamond Light Source) , James N. O'shea (University of Nottingham) , Peter H. Beton (University of Nottingham) , Amber Thompson (University of Oxford) , Harry Anderson (University of Oxford)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry - A European Journal , VOL 20 (40) , PAGES 12826 - 12834

State: Published (Approved)
Published: September 2014
Diamond Proposal Number(s): 7768

Open Access Open Access

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 CH???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 Keywords: Conjugation;Macrocycles;Porphyrinoids;Supramolecular Chemistry;Template Synthesis

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction , I22-Small angle scattering & Diffraction

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