In the quest of Hückel–Hückel and Hückel–Baird double aromatic tropylium (tri)cation and anion derivatives

Besides the most common form of aromaticity involving a π-ring, hexaiodobenzene and hexakis(phenylselenyl)benzene dications also present σ-aromaticity in the outer ring formed by the main group substituents. These two compounds are considered σ- and π-double aromatic, and their characterization is o...

Descripción completa

Detalles Bibliográficos
Autores: Escayola Gordils, Sílvia, Proos Vedin, Nathalie, Poater Teixidor, Albert, Ottosson, Henrik, Solà i Puig, Miquel
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
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:10256/22121
Acceso en línea:http://hdl.handle.net/10256/22121
Access Level:acceso abierto
Palabra clave:Aromaticitat (Química)
Aromaticity (Chemistry)
Funcional de densitat, Teoria del
Density functionals
id ES_2b144e94fb0fa5c8e3cb03acd8fe3c60
oai_identifier_str oai:recercat.cat:10256/22121
network_acronym_str ES
network_name_str España
repository_id_str
spelling In the quest of Hückel–Hückel and Hückel–Baird double aromatic tropylium (tri)cation and anion derivativesEscayola Gordils, SílviaProos Vedin, NathaliePoater Teixidor, AlbertOttosson, HenrikSolà i Puig, MiquelAromaticitat (Química)Aromaticity (Chemistry)Funcional de densitat, Teoria delDensity functionalsBesides the most common form of aromaticity involving a π-ring, hexaiodobenzene and hexakis(phenylselenyl)benzene dications also present σ-aromaticity in the outer ring formed by the main group substituents. These two compounds are considered σ- and π-double aromatic, and their characterization is of special interest to the fields of organic and structural chemistry. In this work, we decided to explore the double aromaticity in substituted tropylium cations for three reasons: (i) the seven neutral halogen substituents of the tropylium cations will, without oxidation, lead to 14 σ-electrons (a 4n + 2 Hückel number); (ii) tropylium cations are highly stable and can be easily generated experimentally; and (iii) whereas in substituted benzenes the distances between substituents in the optimized structures or X-ray crystals are too large to allow strong σ-aromaticity, these distances are expected to be shorter in substituted tropylium cations. Yet, instead of the expected σ-aromaticity, we found that the most stable geometries are highly puckered, meaning that delocalization in both π- and σ-systems is lost. Our results, which include also the tropylium anion and trication in the singlet and triplet state, show that there is a need to open a lone pair hole by oxidation to generate σ-aromaticity. Among the systems studied, only triplet C7Br7+3 with an internal Hückel aromatic tropylium ring and an external incipient Baird aromatic Br7 ring shows double π- and σ-aromaticity. This result, however, is functional-dependent and reveals that 3C7Br73+ is at the borderline for onset of double aromaticityGeneralitat de Catalunya. Grant Number: 2017SGR39 Ministerio de Ciencia e Innovación. Grant Numbers: PID2020-113711GB-I00, PID2021-127423NB-I00 Swedish Research Council. Grant Number: 2019-05618 Universitat de Girona. Grant Number: IFUdG2019 Swedish National Infrastructure for ComputingOpen Access funding provided thanks to the CRUE-CSIC agreement with WileyWileyAgencia Estatal de Investigación2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/22121http://hdl.handle.net/10256/22121Journal of Physical Organic Chemistry, 2023, vol. 36, núm. 1, p. e4447Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1002/poc.4447info:eu-repo/semantics/altIdentifier/issn/0894-3230info:eu-repo/semantics/altIdentifier/eissn/1099-1395PID2020-113711GB-I00PID2021-127423NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113711GB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-127423NB-I00Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/221212026-05-29T05:05:01Z
dc.title.none.fl_str_mv In the quest of Hückel–Hückel and Hückel–Baird double aromatic tropylium (tri)cation and anion derivatives
title In the quest of Hückel–Hückel and Hückel–Baird double aromatic tropylium (tri)cation and anion derivatives
spellingShingle In the quest of Hückel–Hückel and Hückel–Baird double aromatic tropylium (tri)cation and anion derivatives
Escayola Gordils, Sílvia
Aromaticitat (Química)
Aromaticity (Chemistry)
Funcional de densitat, Teoria del
Density functionals
title_short In the quest of Hückel–Hückel and Hückel–Baird double aromatic tropylium (tri)cation and anion derivatives
title_full In the quest of Hückel–Hückel and Hückel–Baird double aromatic tropylium (tri)cation and anion derivatives
title_fullStr In the quest of Hückel–Hückel and Hückel–Baird double aromatic tropylium (tri)cation and anion derivatives
title_full_unstemmed In the quest of Hückel–Hückel and Hückel–Baird double aromatic tropylium (tri)cation and anion derivatives
title_sort In the quest of Hückel–Hückel and Hückel–Baird double aromatic tropylium (tri)cation and anion derivatives
dc.creator.none.fl_str_mv Escayola Gordils, Sílvia
Proos Vedin, Nathalie
Poater Teixidor, Albert
Ottosson, Henrik
Solà i Puig, Miquel
author Escayola Gordils, Sílvia
author_facet Escayola Gordils, Sílvia
Proos Vedin, Nathalie
Poater Teixidor, Albert
Ottosson, Henrik
Solà i Puig, Miquel
author_role author
author2 Proos Vedin, Nathalie
Poater Teixidor, Albert
Ottosson, Henrik
Solà i Puig, Miquel
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación
dc.subject.none.fl_str_mv Aromaticitat (Química)
Aromaticity (Chemistry)
Funcional de densitat, Teoria del
Density functionals
topic Aromaticitat (Química)
Aromaticity (Chemistry)
Funcional de densitat, Teoria del
Density functionals
description Besides the most common form of aromaticity involving a π-ring, hexaiodobenzene and hexakis(phenylselenyl)benzene dications also present σ-aromaticity in the outer ring formed by the main group substituents. These two compounds are considered σ- and π-double aromatic, and their characterization is of special interest to the fields of organic and structural chemistry. In this work, we decided to explore the double aromaticity in substituted tropylium cations for three reasons: (i) the seven neutral halogen substituents of the tropylium cations will, without oxidation, lead to 14 σ-electrons (a 4n + 2 Hückel number); (ii) tropylium cations are highly stable and can be easily generated experimentally; and (iii) whereas in substituted benzenes the distances between substituents in the optimized structures or X-ray crystals are too large to allow strong σ-aromaticity, these distances are expected to be shorter in substituted tropylium cations. Yet, instead of the expected σ-aromaticity, we found that the most stable geometries are highly puckered, meaning that delocalization in both π- and σ-systems is lost. Our results, which include also the tropylium anion and trication in the singlet and triplet state, show that there is a need to open a lone pair hole by oxidation to generate σ-aromaticity. Among the systems studied, only triplet C7Br7+3 with an internal Hückel aromatic tropylium ring and an external incipient Baird aromatic Br7 ring shows double π- and σ-aromaticity. This result, however, is functional-dependent and reveals that 3C7Br73+ is at the borderline for onset of double aromaticity
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/22121
http://hdl.handle.net/10256/22121
url http://hdl.handle.net/10256/22121
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/poc.4447
info:eu-repo/semantics/altIdentifier/issn/0894-3230
info:eu-repo/semantics/altIdentifier/eissn/1099-1395
PID2020-113711GB-I00
PID2021-127423NB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113711GB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-127423NB-I00
dc.rights.none.fl_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv Journal of Physical Organic Chemistry, 2023, vol. 36, núm. 1, p. e4447
Articles publicats (D-Q)
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_ 1869405112722522112
score 15,198674

Similares en LA Referencia