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Int. J. Mol. Sci. 2015, 16(4), 8934-8948;

Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution

Departament de Química, Universitat de les Illes Balears, 07122 Palma de Mallorca, Spain
Catalan Institution for Research and Advanced Studies (ICREA), 08018 Barcelona, Spain
Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Spain
Authors to whom correspondence should be addressed.
Academic Editor: John George Hardy
Received: 27 March 2015 / Revised: 27 March 2015 / Accepted: 14 April 2015 / Published: 22 April 2015
(This article belongs to the Special Issue Supramolecular Interactions)
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In this manuscript we consider from a theoretical point of view the recently reported experimental quantification of anion–π interactions (the attractive force between electron deficient aromatic rings and anions) in solution using aryl extended calix[4]pyrrole receptors as model systems. Experimentally, two series of calix[4]pyrrole receptors functionalized, respectively, with two and four aryl rings at the meso positions, were used to assess the strength of chloride–π interactions in acetonitrile solution. As a result of these studies the contribution of each individual chloride–π interaction was quantified to be very small (<1 kcal/mol). This result is in contrast with the values derived from most theoretical calculations. Herein we report a theoretical study using high-level density functional theory (DFT) calculations that provides a plausible explanation for the observed disagreement between theory and experiment. The study reveals the existence of molecular interactions between solvent molecules and the aromatic walls of the receptors that strongly modulate the chloride–π interaction. In addition, the obtained theoretical results also suggest that the chloride-calix[4]pyrrole complex used as reference to dissect experimentally the contribution of the chloride–π interactions to the total binding energy for both the two and four-wall aryl-extended calix[4]pyrrole model systems is probably not ideal. View Full-Text
Keywords: anion–π interaction; DFT calculations; binding energies anion–π interaction; DFT calculations; binding energies

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Bauzá, A.; Quiñonero, D.; Frontera, A.; Ballester, P. Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution. Int. J. Mol. Sci. 2015, 16, 8934-8948.

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