title: Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host-Guest Systems.
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.
authors.affiliation: 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).|Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364 Lyon (France).
authors.forename: Dawei
authors.initials: D
authors.lastname: Zhang
authors.affiliation: Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364 Lyon (France).|Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille (France).
authors.forename: Bastien
authors.initials: B
authors.lastname: Chatelet
authors.affiliation: Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364 Lyon (France).
authors.forename: Eloisa
authors.initials: E
authors.lastname: Serrano
authors.affiliation: Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364 Lyon (France).
authors.forename: Olivier
authors.initials: O
authors.lastname: Perraud
authors.affiliation: Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364 Lyon (France).
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Dutasta
authors.affiliation: Laboratoire de Chimie Quantique Institut de Chimie, UMR CNRS 7177, Université de Strasbourg, 4, rue Blaise Pascal, 67070 Strasbourg (France). vrobert@unistra.fr.
authors.forename: Vincent
authors.initials: V
authors.lastname: Robert
authors.affiliation: Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364 Lyon (France). alexandre.martinez@centrale-marseille.fr.|Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille (France). alexandre.martinez@centrale-marseille.fr.
authors.forename: Alexandre
authors.initials: A
authors.lastname: Martinez
keywords: anion-π interactions; cooperative effects; fluorine; recognition; supramolecular chemistry