Cations brought together by hydrogen bonds: The protonated pyridine-boronic acid dimer explained

According to the Cambridge Structural Database, protonated pyridine–boronic acid dimers exist in the solid phase, apparently defying repulsive coulombic forces. In order to understand why these cation–cation systems are stable, we carried out M06-2X/6-311++G(3df,2pd) electronic structure calculation...

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Autores: Iribarren, I., Montero-Campillo, M. Merced, Alkorta, Ibon, Elguero, José, Quiñonero, D.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2019
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/183360
Acceso en línea:http://hdl.handle.net/10261/183360
Access Level:acceso abierto
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spelling Cations brought together by hydrogen bonds: The protonated pyridine-boronic acid dimer explainedIribarren, I.Montero-Campillo, M. MercedAlkorta, IbonElguero, JoséQuiñonero, D.According to the Cambridge Structural Database, protonated pyridine–boronic acid dimers exist in the solid phase, apparently defying repulsive coulombic forces. In order to understand why these cation–cation systems are stable, we carried out M06-2X/6-311++G(3df,2pd) electronic structure calculations and used a set of computational tools (energy partitioning, topology of the electron density and electric field maps). The behavior of the charged dimers was compared with the corresponding neutral systems, and the effect of counterions (Br and BF4 ) and the solvent (PCM model) on the binding energies has been considered. In the gas-phase, the charged dimers present positive binding energies but are local minima, with a barrier (16–19 kJ mol1) preventing dissociation. Once the environment is included via solvent effects or counterions, the binding energies become negative; remarkably, the strength of the interaction is very similar in both neutral and charged systems when a polar solvent is considered. Essentially, all methods used evidence that the intermolecular region where the HBs take place is very similar for both neutral and charged dimers. The energy partitioning explains that repulsion and electrostatic terms are compensated by the desolvation and exchange terms in polar solvents, thus giving stability to the charged dimerThanks are given to Dr Ignasi Mata (ICMAB-CSIC) for providing a copy of the program to plot the electric field. This work was carried out with financial support from the Ministerio de Economía, Industria y Competitividad (Projects No. CTQ2015-63997-C2-2-P, CTQ2014-57393-C2-1-P and CTQ2017-85821-R FEDER funds) and Comunidad Autónoma de Madrid (S2013/MIT2841, Fotocarbon).We acknowledge support of the publication fee by the CSIC Open Access Support Initiative through its Unit of Information Resources for Research (URICI)Peer ReviewedRoyal Society of Chemistry (UK)Agencia Estatal de Investigación (España)European CommissionComunidad de MadridMinisterio de Economía y Competitividad (España)Ministerio de Ciencia, Innovación y Universidades (España)Consejo Superior de Investigaciones Científicas (España)Montero-Campillo, M. Merced [0000-0002-9499-0900]Alkorta, Ibon [0000-0001-6876-6211]Elguero, José [0000-0002-9213-6858]Quiñonero, D. [0000-0002-9661-9881]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2019201920192019info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/183360reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#CTQ2017-85821-R/AEI/10.13039/501100011033info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-63997-C2-2-Pinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-57393-C2-1-Pinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/CTQ2017-85821-RS2013/MIT2841/Fotocarbonhttp://dx.doi.org/10.1039/c8cp07542eSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1833602026-05-22T06:33:51Z
dc.title.none.fl_str_mv Cations brought together by hydrogen bonds: The protonated pyridine-boronic acid dimer explained
title Cations brought together by hydrogen bonds: The protonated pyridine-boronic acid dimer explained
spellingShingle Cations brought together by hydrogen bonds: The protonated pyridine-boronic acid dimer explained
Iribarren, I.
title_short Cations brought together by hydrogen bonds: The protonated pyridine-boronic acid dimer explained
title_full Cations brought together by hydrogen bonds: The protonated pyridine-boronic acid dimer explained
title_fullStr Cations brought together by hydrogen bonds: The protonated pyridine-boronic acid dimer explained
title_full_unstemmed Cations brought together by hydrogen bonds: The protonated pyridine-boronic acid dimer explained
title_sort Cations brought together by hydrogen bonds: The protonated pyridine-boronic acid dimer explained
dc.creator.none.fl_str_mv Iribarren, I.
Montero-Campillo, M. Merced
Alkorta, Ibon
Elguero, José
Quiñonero, D.
author Iribarren, I.
author_facet Iribarren, I.
Montero-Campillo, M. Merced
Alkorta, Ibon
Elguero, José
Quiñonero, D.
author_role author
author2 Montero-Campillo, M. Merced
Alkorta, Ibon
Elguero, José
Quiñonero, D.
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación (España)
European Commission
Comunidad de Madrid
Ministerio de Economía y Competitividad (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Consejo Superior de Investigaciones Científicas (España)
Montero-Campillo, M. Merced [0000-0002-9499-0900]
Alkorta, Ibon [0000-0001-6876-6211]
Elguero, José [0000-0002-9213-6858]
Quiñonero, D. [0000-0002-9661-9881]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description According to the Cambridge Structural Database, protonated pyridine–boronic acid dimers exist in the solid phase, apparently defying repulsive coulombic forces. In order to understand why these cation–cation systems are stable, we carried out M06-2X/6-311++G(3df,2pd) electronic structure calculations and used a set of computational tools (energy partitioning, topology of the electron density and electric field maps). The behavior of the charged dimers was compared with the corresponding neutral systems, and the effect of counterions (Br and BF4 ) and the solvent (PCM model) on the binding energies has been considered. In the gas-phase, the charged dimers present positive binding energies but are local minima, with a barrier (16–19 kJ mol1) preventing dissociation. Once the environment is included via solvent effects or counterions, the binding energies become negative; remarkably, the strength of the interaction is very similar in both neutral and charged systems when a polar solvent is considered. Essentially, all methods used evidence that the intermolecular region where the HBs take place is very similar for both neutral and charged dimers. The energy partitioning explains that repulsion and electrostatic terms are compensated by the desolvation and exchange terms in polar solvents, thus giving stability to the charged dimer
publishDate 2019
dc.date.none.fl_str_mv 2019
2019
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/183360
url http://hdl.handle.net/10261/183360
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
CTQ2017-85821-R/AEI/10.13039/501100011033
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-63997-C2-2-P
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-57393-C2-1-P
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/CTQ2017-85821-R
S2013/MIT2841/Fotocarbon
http://dx.doi.org/10.1039/c8cp07542e
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Royal Society of Chemistry (UK)
publisher.none.fl_str_mv Royal Society of Chemistry (UK)
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
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