Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host–Guest Systems |
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| Authors: | Dawei Zhang Dr Bastien Chatelet Eloisa Serrano Dr Olivier Perraud Dr Jean‐Pierre Dutasta Prof Dr Vincent Robert Prof Dr Alexandre Martinez |
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| Affiliation: | 1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, 3663 North Zhongshan Road, Shanghai, 200062 (P. R. China).;2. Laboratoire de Chimie, école Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364 Lyon (France);3. Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille (France);4. Laboratoire de Chimie Quantique Institut de Chimie, UMR CNRS 7177, Université de Strasbourg, 4, rue Blaise Pascal, 67070 Strasbourg (France) |
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| Abstract: | The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation–π and anion–π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron‐poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion‐pair recognition. Wavefunction calculations highlight how short‐ and long‐range interactions interfere in this recognition process, suggesting that a disruption of anion–π interactions can occur in the presence of a co‐bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions. |
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| Keywords: | anion– π interactions cooperative effects fluorine recognition supramolecular chemistry |
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