Cargando…

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

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. Experiment...

Descripción completa

Detalles Bibliográficos
Autores principales: Bauzá, Antonio, Quiñonero, David, Frontera, Antonio, Ballester, Pablo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2015
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4425116/
https://www.ncbi.nlm.nih.gov/pubmed/25913375
http://dx.doi.org/10.3390/ijms16048934
_version_ 1782370446213120000
author Bauzá, Antonio
Quiñonero, David
Frontera, Antonio
Ballester, Pablo
author_facet Bauzá, Antonio
Quiñonero, David
Frontera, Antonio
Ballester, Pablo
author_sort Bauzá, Antonio
collection PubMed
description 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.
format Online
Article
Text
id pubmed-4425116
institution National Center for Biotechnology Information
language English
publishDate 2015
publisher MDPI
record_format MEDLINE/PubMed
spelling pubmed-44251162015-05-20 Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution Bauzá, Antonio Quiñonero, David Frontera, Antonio Ballester, Pablo Int J Mol Sci Article 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. MDPI 2015-04-22 /pmc/articles/PMC4425116/ /pubmed/25913375 http://dx.doi.org/10.3390/ijms16048934 Text en © 2015 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Bauzá, Antonio
Quiñonero, David
Frontera, Antonio
Ballester, Pablo
Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution
title Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution
title_full Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution
title_fullStr Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution
title_full_unstemmed Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution
title_short Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution
title_sort reconciling experiment and theory in the use of aryl-extended calix[4]pyrrole receptors for the experimental quantification of chloride–π interactions in solution
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4425116/
https://www.ncbi.nlm.nih.gov/pubmed/25913375
http://dx.doi.org/10.3390/ijms16048934
work_keys_str_mv AT bauzaantonio reconcilingexperimentandtheoryintheuseofarylextendedcalix4pyrrolereceptorsfortheexperimentalquantificationofchloridepinteractionsinsolution
AT quinonerodavid reconcilingexperimentandtheoryintheuseofarylextendedcalix4pyrrolereceptorsfortheexperimentalquantificationofchloridepinteractionsinsolution
AT fronteraantonio reconcilingexperimentandtheoryintheuseofarylextendedcalix4pyrrolereceptorsfortheexperimentalquantificationofchloridepinteractionsinsolution
AT ballesterpablo reconcilingexperimentandtheoryintheuseofarylextendedcalix4pyrrolereceptorsfortheexperimentalquantificationofchloridepinteractionsinsolution