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...
Autores principales: | , , , |
---|---|
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 |