Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 40, Pages 12826-12834Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201403714
Keywords
conjugation; macrocycles; porphyrinoids; supramolecular chemistry; template synthesis
Categories
Funding
- Engineering and Physical Sciences Research Council (EPSRC) [MT7768]
- European Research Council [320969]
- Clarendon Fund of the University of Oxford
- Engineering and Physical Sciences Research Council [EP/J007161/1, EP/J006939/1] Funding Source: researchfish
- EPSRC [EP/J006939/1, EP/J007161/1] Funding Source: UKRI
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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 degrees between the planes of the two template units. The crystal structure reveals many unexpected intramolecular C-H center dot center dot center dot 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.
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