Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings?

Compounds that can be labeled as “aromatic chameleons” are π-conjugated compounds that are able to adjust their π-electron distributions so as to comply with the different rules of aromaticity in different electronic states. We used quantum chemical calculations to explore how the fusion of benzene...

ver descrição completa

Detalhes bibliográficos
Autores: Ayub, Rabia, El Bakouri, Ouissam, Jorner, Kjell, Solà i Puig, Miquel, Ottosson, Henrik
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Recursos: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:10256/18716
Acesso em linha:http://hdl.handle.net/10256/18716
Access Level:acceso abierto
Palavra-chave:Aromaticitat (Química)
Aromaticity (Chemistry)
id ES_cbd22c7b2d0d26f5e1cc19d1b5bccfe6
oai_identifier_str oai:recercat.cat:10256/18716
network_acronym_str ES
network_name_str España
repository_id_str
spelling Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings?Ayub, RabiaEl Bakouri, OuissamJorner, KjellSolà i Puig, MiquelOttosson, HenrikAromaticitat (Química)Aromaticity (Chemistry)Compounds that can be labeled as “aromatic chameleons” are π-conjugated compounds that are able to adjust their π-electron distributions so as to comply with the different rules of aromaticity in different electronic states. We used quantum chemical calculations to explore how the fusion of benzene rings onto aromatic chameleonic units represented by biphenylene, dibenzocyclooctatetraene, and dibenzo[a,e]pentalene modifies the first triplet excited states (T1) of the compounds. Decreases in T1 energies are observed when going from isomers with linear connectivity of the fused benzene rings to those with cis- or trans-bent connectivities. The T1 energies decreased down to those of the parent (isolated) 4nπ-electron units. Simultaneously, we observe an increased influence of triplet state aromaticity of the central 4n ring as given by Baird’s rule and evidenced by geometric, magnetic, and electron density based aromaticity indices (HOMA, NICS-XY, ACID, and FLU). Because of an influence of triplet state aromaticity in the central 4nπ-electron units, the most stabilized compounds retain the triplet excitation in Baird π-quartets or octets, enabling the outer benzene rings to adapt closed-shell singlet Clar π-sextet character. Interestingly, the T1 energies go down as the total number of aromatic cycles within a molecule in the T1 state increasesThe Erasmus Mundus EXPERTS III is acknowledged for a PhD scholarship to RA and the Swedish Research Council (Vetenskapsrådet) are acknowledged for financial support. The Swedish infrastructure for computing (SNIC) at NSC and UPPMAX (SNIC-2016-1-74 and SNIC-2016/7-21) are greatly acknowledged for the generous allotment of computer time. M.S. and O.E.B. acknowledges the Ministerio de Economía y Competitividad (MINECO) of Spain (Project CTQ2014-54306-P), the Generalitat de Catalunya (project 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, ICREA Academia 2014 prize for M.S., and grant No. 2014FI_B 00429 to O.E.B.), and the EU under the FEDER grant UNGI10-4E-801 (European Fund for Regional Development)American Chemical Society (ACS)Ministerio de Economía y Competitividad (Espanya)2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionpeer-reviewed14 p.application/pdfhttp://hdl.handle.net/10256/18716http://hdl.handle.net/10256/18716© Journal of Organic Chemistry, 2017, vol. 82, núm. 12, p. 6327-6340Articles publicats (D-Q)Ayub, Rabia El Bakouri, Ouissam Jorner, Kjell Solà i Puig, Miquel Ottosson, Henrik 2017 Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings? Journal of Organic Chemistry 82 12 6327 6340reponame: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/10.1021/acs.joc.7b00906info:eu-repo/semantics/altIdentifier/issn/0022-3263info:eu-repo/semantics/altIdentifier/eissn/1520-6904info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-PTots els drets reservatsinfo:eu-repo/semantics/openAccessoai:recercat.cat:10256/187162026-05-29T05:05:01Z
dc.title.none.fl_str_mv Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings?
title Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings?
spellingShingle Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings?
Ayub, Rabia
Aromaticitat (Química)
Aromaticity (Chemistry)
title_short Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings?
title_full Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings?
title_fullStr Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings?
title_full_unstemmed Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings?
title_sort Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings?
dc.creator.none.fl_str_mv Ayub, Rabia
El Bakouri, Ouissam
Jorner, Kjell
Solà i Puig, Miquel
Ottosson, Henrik
author Ayub, Rabia
author_facet Ayub, Rabia
El Bakouri, Ouissam
Jorner, Kjell
Solà i Puig, Miquel
Ottosson, Henrik
author_role author
author2 El Bakouri, Ouissam
Jorner, Kjell
Solà i Puig, Miquel
Ottosson, Henrik
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (Espanya)
dc.subject.none.fl_str_mv Aromaticitat (Química)
Aromaticity (Chemistry)
topic Aromaticitat (Química)
Aromaticity (Chemistry)
description Compounds that can be labeled as “aromatic chameleons” are π-conjugated compounds that are able to adjust their π-electron distributions so as to comply with the different rules of aromaticity in different electronic states. We used quantum chemical calculations to explore how the fusion of benzene rings onto aromatic chameleonic units represented by biphenylene, dibenzocyclooctatetraene, and dibenzo[a,e]pentalene modifies the first triplet excited states (T1) of the compounds. Decreases in T1 energies are observed when going from isomers with linear connectivity of the fused benzene rings to those with cis- or trans-bent connectivities. The T1 energies decreased down to those of the parent (isolated) 4nπ-electron units. Simultaneously, we observe an increased influence of triplet state aromaticity of the central 4n ring as given by Baird’s rule and evidenced by geometric, magnetic, and electron density based aromaticity indices (HOMA, NICS-XY, ACID, and FLU). Because of an influence of triplet state aromaticity in the central 4nπ-electron units, the most stabilized compounds retain the triplet excitation in Baird π-quartets or octets, enabling the outer benzene rings to adapt closed-shell singlet Clar π-sextet character. Interestingly, the T1 energies go down as the total number of aromatic cycles within a molecule in the T1 state increases
publishDate 2017
dc.date.none.fl_str_mv 2017
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/10256/18716
http://hdl.handle.net/10256/18716
url http://hdl.handle.net/10256/18716
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.7b00906
info:eu-repo/semantics/altIdentifier/issn/0022-3263
info:eu-repo/semantics/altIdentifier/eissn/1520-6904
info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-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 14 p.
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv © Journal of Organic Chemistry, 2017, vol. 82, núm. 12, p. 6327-6340
Articles publicats (D-Q)
Ayub, Rabia El Bakouri, Ouissam Jorner, Kjell Solà i Puig, Miquel Ottosson, Henrik 2017 Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n+2)π-Rings? Journal of Organic Chemistry 82 12 6327 6340
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_ 1869419621863391232
score 15,811543

Registos relacionados