Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride-pi Interaction

<p> In this manuscript we consider from a theoretical point of view the recently reported experimental quantification of anion- interactions (the attractive force between electron deficient aromatic rings and anions) in solution using aryl extended calix[4]pyrrole receptors as model systems. E...

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Detalles Bibliográficos
Autores: Bauza, Antonio, Quinonero, David, Frontera, Antonio, Ballester, Pablo
Tipo de recurso: artículo
Fecha de publicación:2015
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/305856
Acceso en línea:http://hdl.handle.net/2072/305856
https://doi.org/10.3390/ijms16048934
Access Level:acceso abierto
Palabra clave:anion- interaction
DFT calculations
binding energies
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spelling Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride-pi InteractionBauza, AntonioQuinonero, DavidFrontera, AntonioBallester, Pabloanion- interactionDFT calculationsbinding energies<p> In this manuscript we consider from a theoretical point of view the recently reported experimental quantification of anion- 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- interactions in acetonitrile solution. As a result of these studies the contribution of each individual chloride- interaction was quantified to be very small (&lt;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- 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- interactions to the total binding energy for both the two and four-wall aryl-extended calix[4]pyrrole model systems is probably not ideal.</p>MDPI AG2015info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/2072/305856https://doi.org/10.3390/ijms16048934RECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésMINECOProyecto de Investigación Fundamental no orientadaSevero Ochoa Excellence Accreditation 2014-2018CONSOLIDER INGENIO 2010MOLCONTAINER--International Journal of Molecular SciencesCTQ2011-23014SEV-2013-0319CSD2010-00065©MDPIinfo:eu-repo/semantics/openAccessoai:recercat.cat:2072/3058562026-05-29T05:05:01Z
dc.title.none.fl_str_mv Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride-pi Interaction
title Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride-pi Interaction
spellingShingle Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride-pi Interaction
Bauza, Antonio
anion- interaction
DFT calculations
binding energies
title_short Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride-pi Interaction
title_full Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride-pi Interaction
title_fullStr Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride-pi Interaction
title_full_unstemmed Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride-pi Interaction
title_sort Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride-pi Interaction
dc.creator.none.fl_str_mv Bauza, Antonio
Quinonero, David
Frontera, Antonio
Ballester, Pablo
author Bauza, Antonio
author_facet Bauza, Antonio
Quinonero, David
Frontera, Antonio
Ballester, Pablo
author_role author
author2 Quinonero, David
Frontera, Antonio
Ballester, Pablo
author2_role author
author
author
dc.subject.none.fl_str_mv anion- interaction
DFT calculations
binding energies
topic anion- interaction
DFT calculations
binding energies
description <p> In this manuscript we consider from a theoretical point of view the recently reported experimental quantification of anion- 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- interactions in acetonitrile solution. As a result of these studies the contribution of each individual chloride- interaction was quantified to be very small (&lt;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- 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- interactions to the total binding energy for both the two and four-wall aryl-extended calix[4]pyrrole model systems is probably not ideal.</p>
publishDate 2015
dc.date.none.fl_str_mv 2015
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/2072/305856
https://doi.org/10.3390/ijms16048934
url http://hdl.handle.net/2072/305856
https://doi.org/10.3390/ijms16048934
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv MINECO
Proyecto de Investigación Fundamental no orientada
Severo Ochoa Excellence Accreditation 2014-2018
CONSOLIDER INGENIO 2010
MOLCONTAINER
-
-
International Journal of Molecular Sciences
CTQ2011-23014
SEV-2013-0319
CSD2010-00065
dc.rights.none.fl_str_mv ©MDPI
info:eu-repo/semantics/openAccess
rights_invalid_str_mv ©MDPI
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv MDPI AG
publisher.none.fl_str_mv MDPI AG
dc.source.none.fl_str_mv RECERCAT (Dipòsit de la Recerca de Catalunya)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.812429

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