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Direct Experimental Evidence for Halogen–Aryl π Interactions in Solution from Molecular Torsion Balances |
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| Authors: | Dr Han Sun Dr André Horatscheck Dr Vera Martos M Sc Max Bartetzko Dr Ulrike Uhrig Prof Dr Dieter Lentz Dr Peter Schmieder Dr Marc Nazaré |
| Institution: | 1. Departments of Chemical Biology and Structural Biology, Leibniz-Institut fϋr Molekulare Pharmakologie (FMP), Campus Berlin-Buch, Robert-Roessle-Strasse 10, 13125 Berlin, Germany
These authors contributed equally.;2. Departments of Chemical Biology and Structural Biology, Leibniz-Institut fϋr Molekulare Pharmakologie (FMP), Campus Berlin-Buch, Robert-Roessle-Strasse 10, 13125 Berlin, Germany Drug Discovery and Development Centre (H3D), Department of Chemistry, University of Cape Town, Rondebosch, 7701 South Africa These authors contributed equally.;3. Departments of Chemical Biology and Structural Biology, Leibniz-Institut fϋr Molekulare Pharmakologie (FMP), Campus Berlin-Buch, Robert-Roessle-Strasse 10, 13125 Berlin, Germany;4. Departments of Chemical Biology and Structural Biology, Leibniz-Institut fϋr Molekulare Pharmakologie (FMP), Campus Berlin-Buch, Robert-Roessle-Strasse 10, 13125 Berlin, Germany Max-Planck-Institut für Kolloid- und Grenzflächenforschung, Am Mühlenberg 1, 14476 Potsdam, Germany;5. European Molecular Biology Laboratory (EMBL), Chemical Biology Core Facility, Meyerhofstrasse 1, 69117 Heidelberg, Germany;6. Institut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstrasse 34–36, 14195 Berlin, Germany |
| Abstract: | We dissected halogen–aryl π interactions experimentally using a bicyclic N-arylimide based molecular torsion balances system, which is based on the influence of the non-bonded interaction on the equilibria between folded and unfolded states. Through comparison of balances modulated by higher halogens with fluorine balances, we determined the magnitude of the halogen–aryl π interactions in our unimolecular systems to be larger than −5.0 kJ mol−1, which is comparable with the magnitude estimated in the biomolecular systems. Our study provides direct experimental evidence of halogen–aryl π interactions in solution, which until now have only been revealed in the solid state and evaluated theoretically by quantum-mechanical calculations. |
| Keywords: | Dipolare Restkopplungen Halogenbrücken Halogen-Aryl-Wechselwirkungen Molekulare Erkennung Molekulare Waagen |