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Chemphyschem. 2015 Oct 5;16(14):2931-5. doi: 10.1002/cphc.201500610. Epub 2015 Aug 25.

Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host-Guest Systems.

Author information

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). vrobert@unistra.fr.
5
Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364 Lyon (France). alexandre.martinez@centrale-marseille.fr.
6
Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille (France). alexandre.martinez@centrale-marseille.fr.

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.

KEYWORDS:

anion-π interactions; cooperative effects; fluorine; recognition; supramolecular chemistry

PMID:
26401973
DOI:
10.1002/cphc.201500610

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