Allosteric Cooperativity and Template-Directed Synthesis with Stacked Ligands in Porphyrin Nanorings
The link between allosteric cooperativity and template-directed synthesis has been investigated by studying complexes in which two oligopyridine ligands bind inside a zinc porphyrin nanoring in a stacked arrangement. The binding of a 6-porphyrin nanoring to two tridentate ligands (with s-triazine or benzene cores) occurs with high negative allosteric cooperativity (α ≈ 10-3-10-4). Formation constants for 1:1 and 1:2 complexes were determined by UV-vis-NIR denaturation titration, using pyridine as a competing ligand, and cooperativity factors were confirmed by NMR spectroscopy. The rate constants for formation of the 1:1 and 1:2 complexes are approximately equal, and the negative cooperativity can be attributed to faster dissociation of the 1:2 complex. These tridentate ligands are not effective templates for directing the synthesis of the 6-porphyrin nanoring, in keeping with their negative cooperativity of binding. In contrast, the binding of a 12-porphyrin nanoring to two hexadentate ligands occurs with high positive allosteric cooperativity (α > 40), and the ligand is an effective Vernier template for directing the synthesis of the 12-porphyrin nanoring. This stacked Vernier template approach creates the product in an open circular conformation, which is advantageous for preparing macrocycles that do not easily adopt a figure-of-eight geometry.
Medienart: |
E-Artikel |
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Erscheinungsjahr: |
2020 |
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Erschienen: |
2020 |
Enthalten in: |
Zur Gesamtaufnahme - volume:142 |
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Enthalten in: |
Journal of the American Chemical Society - 142(2020), 30 vom: 29. Juli, Seite 13219-13226 |
Sprache: |
Englisch |
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Beteiligte Personen: |
Bols, Pernille S [VerfasserIn] |
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Anmerkungen: |
Date Completed 12.01.2021 Date Revised 12.01.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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doi: |
10.1021/jacs.0c06269 |
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funding: |
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Förderinstitution / Projekttitel: |
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PPN (Katalog-ID): |
NLM312107730 |
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520 | |a The link between allosteric cooperativity and template-directed synthesis has been investigated by studying complexes in which two oligopyridine ligands bind inside a zinc porphyrin nanoring in a stacked arrangement. The binding of a 6-porphyrin nanoring to two tridentate ligands (with s-triazine or benzene cores) occurs with high negative allosteric cooperativity (α ≈ 10-3-10-4). Formation constants for 1:1 and 1:2 complexes were determined by UV-vis-NIR denaturation titration, using pyridine as a competing ligand, and cooperativity factors were confirmed by NMR spectroscopy. The rate constants for formation of the 1:1 and 1:2 complexes are approximately equal, and the negative cooperativity can be attributed to faster dissociation of the 1:2 complex. These tridentate ligands are not effective templates for directing the synthesis of the 6-porphyrin nanoring, in keeping with their negative cooperativity of binding. In contrast, the binding of a 12-porphyrin nanoring to two hexadentate ligands occurs with high positive allosteric cooperativity (α > 40), and the ligand is an effective Vernier template for directing the synthesis of the 12-porphyrin nanoring. This stacked Vernier template approach creates the product in an open circular conformation, which is advantageous for preparing macrocycles that do not easily adopt a figure-of-eight geometry | ||
650 | 4 | |a Journal Article | |
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700 | 1 | |a Rickhaus, Michel |e verfasserin |4 aut | |
700 | 1 | |a Tejerina, Lara |e verfasserin |4 aut | |
700 | 1 | |a Gotfredsen, Henrik |e verfasserin |4 aut | |
700 | 1 | |a Eriksen, Kristina |e verfasserin |4 aut | |
700 | 1 | |a Jirasek, Michael |e verfasserin |4 aut | |
700 | 1 | |a Anderson, Harry L |e verfasserin |4 aut | |
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