Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-Porphyrin nanoring
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 s...
| Main Authors: | , , , , , , , , , |
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| Format: | Article |
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Wiley-VCH Verlag
2014
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| Online Access: | https://eprints.nottingham.ac.uk/34935/ |
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| author | 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. |
| author_facet | 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. |
| author_sort | Kondratuk, Dmitry V. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T19:24:34Z |
| format | Article |
| id | nottingham-34935 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:24:34Z |
| publishDate | 2014 |
| publisher | Wiley-VCH Verlag |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-349352020-05-04T16:52:07Z https://eprints.nottingham.ac.uk/34935/ 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. 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. Wiley-VCH Verlag 2014-08-25 Article PeerReviewed 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. 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 Conjugation Macrocycles Porphyrinoids Supramolecular chemistry Template synthesis http://dx.doi.org/10.1002/chem.201403714 doi:10.1002/chem.201403714 doi:10.1002/chem.201403714 |
| spellingShingle | Conjugation Macrocycles Porphyrinoids Supramolecular chemistry Template synthesis 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. Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-Porphyrin nanoring |
| title | Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-Porphyrin nanoring |
| title_full | Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-Porphyrin nanoring |
| title_fullStr | Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-Porphyrin nanoring |
| title_full_unstemmed | Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-Porphyrin nanoring |
| title_short | Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-Porphyrin nanoring |
| title_sort | vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-porphyrin nanoring |
| topic | Conjugation Macrocycles Porphyrinoids Supramolecular chemistry Template synthesis |
| url | https://eprints.nottingham.ac.uk/34935/ https://eprints.nottingham.ac.uk/34935/ https://eprints.nottingham.ac.uk/34935/ |