Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?

The larger stability of phenacenes compared to their acene isomers in their ground states is attributed to the larger aromaticity of the former. To our knowledge the relative stability of acenes and phenacenes in their lowest-lying triplet states (T1) has not been discussed yet. Using unrestricted d...

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Detalhes bibliográficos
Autores: Pino-Rios, Ricardo, Báez-Grez, Rodrigo, Solà i Puig, Miquel
Tipo de documento: artigo
Estado:Versión aceptada para publicación
Data de publicação:2021
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositório:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/19773
Acesso em linha:http://hdl.handle.net/10256/19773
Access Level:Acceso aberto
Palavra-chave:Aromaticitat (Química)
Aromaticity (Chemistry)
Acens
Acenes
Fenacens
Phenacenes
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spelling Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?Pino-Rios, RicardoBáez-Grez, RodrigoSolà i Puig, MiquelAromaticitat (Química)Aromaticity (Chemistry)AcensAcenesFenacensPhenacenesThe larger stability of phenacenes compared to their acene isomers in their ground states is attributed to the larger aromaticity of the former. To our knowledge the relative stability of acenes and phenacenes in their lowest-lying triplet states (T1) has not been discussed yet. Using unrestricted density functional theory calculations, our results show that for the smallests members of the series, acenes in their T1 states are more stable than the corresponding phenacenes. However, when the number of the rings (n) involved increases, the energy difference is reduced and for n > 12, phenacenes become more stable than acenes in their T1 states. To rationalize this trend, we analyze the aromaticity of acenes and phenacenes using a set of aromaticity descriptors. We find that in the T1 states of both acenes and phenacenes, the outer rings form aromatic Clar π-sextets. In acenes, delocalization of spin density in the central rings leads to the preferred formation of the largest antiaromatic diradical. Resonant structures in the form of antiaromatic diradical Baird π-octadectets and π-tetradectets are the major contributors, while the smaller ones, such as π-doublets and π-sextets, contribute the least. In phenacenes, structures with diradical antiaromatic Baird π-sextets in some of the central rings contribute the most. These results are relevant to understand the (anti)aromaticity of larger polycyclic aromatic hydrocarbons in their triplet statesR.B-G. is grateful for the financial support of FONDECYT Postdoctorado 3210037. Powered@NLHPC. This research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02). M.S. acknowledges the financial support from the Ministerio de Economía y Competitividad of Spain (project CTQ2017-85341-P) and the Generalitat de Catalunya (project 2017SGR39)Royal Society of Chemistry (RSC)Agencia Estatal de Investigacióninfo2021info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionpeer-reviewed9 p.application/pdfhttp://hdl.handle.net/10256/19773http://hdl.handle.net/10256/19773© Physical Chemistry Chemical Physics, 2021, vol. 23, p. 13574-13582Articles publicats (D-Q)Pino-Rios, Ricardo Báez-Grez, Rodrigo Solà i Puig, Miquel 2021 Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight? Physical Chemistry Chemical Physics 23 13574 13582reponame: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/10.1039/D1CP01441Binfo:eu-repo/semantics/altIdentifier/issn/1463-9076info:eu-repo/semantics/altIdentifier/eissn/1463-9084info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-85341-PTots els drets reservatsinfo:eu-repo/semantics/openAccessoai:recercat.cat:10256/197732026-05-29T05:05:01Z
dc.title.none.fl_str_mv Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?
title Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?
spellingShingle Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?
Pino-Rios, Ricardo
Aromaticitat (Química)
Aromaticity (Chemistry)
Acens
Acenes
Fenacens
Phenacenes
title_short Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?
title_full Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?
title_fullStr Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?
title_full_unstemmed Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?
title_sort Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?
dc.creator.none.fl_str_mv Pino-Rios, Ricardo
Báez-Grez, Rodrigo
Solà i Puig, Miquel
author Pino-Rios, Ricardo
author_facet Pino-Rios, Ricardo
Báez-Grez, Rodrigo
Solà i Puig, Miquel
author_role author
author2 Báez-Grez, Rodrigo
Solà i Puig, Miquel
author2_role author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación
dc.subject.none.fl_str_mv Aromaticitat (Química)
Aromaticity (Chemistry)
Acens
Acenes
Fenacens
Phenacenes
topic Aromaticitat (Química)
Aromaticity (Chemistry)
Acens
Acenes
Fenacens
Phenacenes
description The larger stability of phenacenes compared to their acene isomers in their ground states is attributed to the larger aromaticity of the former. To our knowledge the relative stability of acenes and phenacenes in their lowest-lying triplet states (T1) has not been discussed yet. Using unrestricted density functional theory calculations, our results show that for the smallests members of the series, acenes in their T1 states are more stable than the corresponding phenacenes. However, when the number of the rings (n) involved increases, the energy difference is reduced and for n > 12, phenacenes become more stable than acenes in their T1 states. To rationalize this trend, we analyze the aromaticity of acenes and phenacenes using a set of aromaticity descriptors. We find that in the T1 states of both acenes and phenacenes, the outer rings form aromatic Clar π-sextets. In acenes, delocalization of spin density in the central rings leads to the preferred formation of the largest antiaromatic diradical. Resonant structures in the form of antiaromatic diradical Baird π-octadectets and π-tetradectets are the major contributors, while the smaller ones, such as π-doublets and π-sextets, contribute the least. In phenacenes, structures with diradical antiaromatic Baird π-sextets in some of the central rings contribute the most. These results are relevant to understand the (anti)aromaticity of larger polycyclic aromatic hydrocarbons in their triplet states
publishDate 2021
dc.date.none.fl_str_mv 2021
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
peer-reviewed
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/19773
http://hdl.handle.net/10256/19773
url http://hdl.handle.net/10256/19773
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/D1CP01441B
info:eu-repo/semantics/altIdentifier/issn/1463-9076
info:eu-repo/semantics/altIdentifier/eissn/1463-9084
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-85341-P
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 9 p.
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry (RSC)
publisher.none.fl_str_mv Royal Society of Chemistry (RSC)
dc.source.none.fl_str_mv © Physical Chemistry Chemical Physics, 2021, vol. 23, p. 13574-13582
Articles publicats (D-Q)
Pino-Rios, Ricardo Báez-Grez, Rodrigo Solà i Puig, Miquel 2021 Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight? Physical Chemistry Chemical Physics 23 13574 13582
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 15,811543

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