Quantification of CH-pi Interactions Using Calix[4]pyrrole Receptors as Model Systems

<p> We describe the use of two series of aryl-extended calix[4]pyrrole receptors bearing two and four electronically tunable phenyl groups, respectively, in their meso-positions as model systems for the quantification of CH-pi interactions in solution. The &quot;four-wall&quot; and the...

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Authors: Aragay, Gemma, Hernández, Daniel, Verdejo, Begoña, Escudero-Adán, Eduardo C., Martínez, Marta, Ballester, Pablo
Format: article
Publication Date:2015
Country:España
Institution:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repository:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/305817
Online Access:http://hdl.handle.net/2072/305817
https://doi.org/10.3390/molecules200916672
Access Level:Open access
Keyword:ch- interactions
calix[4]pyrrole
trimethylamineoxide
trimethylphosphine oxide
electrostatic forces dispersion forces
face aromatic interactions
anion-binding properties
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oai_identifier_str oai:recercat.cat:2072/305817
network_acronym_str ES
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repository_id_str
spelling Quantification of CH-pi Interactions Using Calix[4]pyrrole Receptors as Model SystemsAragay, GemmaHernández, DanielVerdejo, BegoñaEscudero-Adán, Eduardo C.Martínez, MartaBallester, Pabloch- interactionscalix[4]pyrroletrimethylamineoxidetrimethylphosphine oxideelectrostatic forces dispersion forcesface aromatic interactionsanion-binding properties<p> We describe the use of two series of aryl-extended calix[4]pyrrole receptors bearing two and four electronically tunable phenyl groups, respectively, in their meso-positions as model systems for the quantification of CH-pi interactions in solution. The &quot;four-wall&quot; and the &quot;two-wall&quot; receptors formed thermodynamically stable 1:1 complexes in acetonitrile solution with both trimethylamine N-oxide and trimethylphosphine P-oxide as guests. The complexes were mainly stabilized by the formation of four convergent hydrogen bonds between the oxygen atom of the guests and the pyrrole NHs of the host. In general, the N-oxide produced thermodynamically more stable hydrogen bonding interactions than the P-oxide. Upon guest binding, the receptors adopted the cone conformation and the methyl groups of the included guests engaged in CH-pi interactions with the aromatic walls. We show that the modification of the electronic properties of the aromatic surfaces, in any of the receptor series, did not have a significant impact in the measured binding affinities for a given guest. However, the larger binding affinities determined for the &quot;four-wall&quot; receptors in comparison to the &quot;two-wall&quot; counterparts supported the importance of CH-pi interactions on guest complexation. The strength of the CH-pi interactions present in the inclusion complexes was quantified employing the octamethyl calix[4]pyrrole as reference. We determined an average magnitude of similar to 1 kcal.mol(-1) for each CH-pi interaction. The CH-pi interactions featured a reduced electrostatic nature and thus dispersion forces were assigned as main contributors of their strength.</p>MDPI AG2015info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/2072/305817https://doi.org/10.3390/molecules200916672RECERCAT (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)InglésMINECOPrograma Estatal de I+D+i Orientada a los Retos de la SociedadPROYECTO CONSOLIDERSevero Ochoa Excellence Accreditation 2014-2018SENSOSALUDRedINTECATMoleculesCTQ2014-56295-RCTQ2014-52974-REDCSEV-2013-0319© MDPIinfo:eu-repo/semantics/openAccessoai:recercat.cat:2072/3058172026-05-29T05:05:01Z
dc.title.none.fl_str_mv Quantification of CH-pi Interactions Using Calix[4]pyrrole Receptors as Model Systems
title Quantification of CH-pi Interactions Using Calix[4]pyrrole Receptors as Model Systems
spellingShingle Quantification of CH-pi Interactions Using Calix[4]pyrrole Receptors as Model Systems
Aragay, Gemma
ch- interactions
calix[4]pyrrole
trimethylamineoxide
trimethylphosphine oxide
electrostatic forces dispersion forces
face aromatic interactions
anion-binding properties
title_short Quantification of CH-pi Interactions Using Calix[4]pyrrole Receptors as Model Systems
title_full Quantification of CH-pi Interactions Using Calix[4]pyrrole Receptors as Model Systems
title_fullStr Quantification of CH-pi Interactions Using Calix[4]pyrrole Receptors as Model Systems
title_full_unstemmed Quantification of CH-pi Interactions Using Calix[4]pyrrole Receptors as Model Systems
title_sort Quantification of CH-pi Interactions Using Calix[4]pyrrole Receptors as Model Systems
dc.creator.none.fl_str_mv Aragay, Gemma
Hernández, Daniel
Verdejo, Begoña
Escudero-Adán, Eduardo C.
Martínez, Marta
Ballester, Pablo
author Aragay, Gemma
author_facet Aragay, Gemma
Hernández, Daniel
Verdejo, Begoña
Escudero-Adán, Eduardo C.
Martínez, Marta
Ballester, Pablo
author_role author
author2 Hernández, Daniel
Verdejo, Begoña
Escudero-Adán, Eduardo C.
Martínez, Marta
Ballester, Pablo
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv ch- interactions
calix[4]pyrrole
trimethylamineoxide
trimethylphosphine oxide
electrostatic forces dispersion forces
face aromatic interactions
anion-binding properties
topic ch- interactions
calix[4]pyrrole
trimethylamineoxide
trimethylphosphine oxide
electrostatic forces dispersion forces
face aromatic interactions
anion-binding properties
description <p> We describe the use of two series of aryl-extended calix[4]pyrrole receptors bearing two and four electronically tunable phenyl groups, respectively, in their meso-positions as model systems for the quantification of CH-pi interactions in solution. The &quot;four-wall&quot; and the &quot;two-wall&quot; receptors formed thermodynamically stable 1:1 complexes in acetonitrile solution with both trimethylamine N-oxide and trimethylphosphine P-oxide as guests. The complexes were mainly stabilized by the formation of four convergent hydrogen bonds between the oxygen atom of the guests and the pyrrole NHs of the host. In general, the N-oxide produced thermodynamically more stable hydrogen bonding interactions than the P-oxide. Upon guest binding, the receptors adopted the cone conformation and the methyl groups of the included guests engaged in CH-pi interactions with the aromatic walls. We show that the modification of the electronic properties of the aromatic surfaces, in any of the receptor series, did not have a significant impact in the measured binding affinities for a given guest. However, the larger binding affinities determined for the &quot;four-wall&quot; receptors in comparison to the &quot;two-wall&quot; counterparts supported the importance of CH-pi interactions on guest complexation. The strength of the CH-pi interactions present in the inclusion complexes was quantified employing the octamethyl calix[4]pyrrole as reference. We determined an average magnitude of similar to 1 kcal.mol(-1) for each CH-pi interaction. The CH-pi interactions featured a reduced electrostatic nature and thus dispersion forces were assigned as main contributors of their strength.</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/2072/305817
https://doi.org/10.3390/molecules200916672
url http://hdl.handle.net/2072/305817
https://doi.org/10.3390/molecules200916672
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv MINECO
Programa Estatal de I+D+i Orientada a los Retos de la Sociedad
PROYECTO CONSOLIDER
Severo Ochoa Excellence Accreditation 2014-2018
SENSOSALUD
RedINTECAT
Molecules
CTQ2014-56295-R
CTQ2014-52974-REDC
SEV-2013-0319
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
_version_ 1869407190964502528
score 15,812455

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