Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds

Due to the reversal in electron counts for aromaticity and antiaromaticity in the closed-shell singlet state (normally ground state, S0) and lowest * triplet state (T1 or T0), as given by Hückel's and Baird's rules, respectively, fulvenes are influenced by their substituents in the oppos...

Descripción completa

Detalles Bibliográficos
Autores: Yadav, Sangeeta, El Bakouri, Ouissam, Jorner, Kjell, Tong, Hui, Dahlstrand, Christian, Solà i Puig, Miquel, Ottosson, Henrik
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
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:10256/16653
Acceso en línea:http://hdl.handle.net/10256/16653
Access Level:acceso abierto
Palabra clave:Aromaticitat (Química)
Aromaticity (Chemistry)
Química quàntica
Quantum chemistry
id ES_947842dc0296c2c279c66a41b01ac957
oai_identifier_str oai:recercat.cat:10256/16653
network_acronym_str ES
network_name_str España
repository_id_str
spelling Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State CompoundsYadav, SangeetaEl Bakouri, OuissamJorner, KjellTong, HuiDahlstrand, ChristianSolà i Puig, MiquelOttosson, HenrikAromaticitat (Química)Aromaticity (Chemistry)Química quànticaQuantum chemistryDue to the reversal in electron counts for aromaticity and antiaromaticity in the closed-shell singlet state (normally ground state, S0) and lowest * triplet state (T1 or T0), as given by Hückel's and Baird's rules, respectively, fulvenes are influenced by their substituents in the opposite manner in the T1 and S0 states. This effect is caused by a reversal in the dipole moment when going from S0 to T1 as fulvenes adapt to the difference in electron counts for aromaticity in various states; they are aromatic chameleons. Thus, a substituent pattern that enhances (reduces) fulvene aromaticity in S0 reduces (enhances) aromaticity in T1, allowing for rationalizations of the triplet state energies (ET) of substituted fulvenes. Through quantum chemical calculations we now assess which substituents and which positions on the pentafulvene core are the most powerful for designing compounds with low or inverted ET. As a means to increase the -electron withdrawing capacity of cyano groups we found that protonation at the cyano N atoms of 6,6-dicyanopentafulvenes can be a route to on-demand formation of a fulvenium dication with a triplet ground state (T0). The five-membered ring of this species is markedly Baird-aromatic, although less than the cyclopentadienyl cation known to have a Baird-aromatic T0 stateM.S. is grateful for financial support from the Spanish MINECO (project CTQ2017-85341-P), the Catalan DIUE (2017SGR39, XRQTC, and ICREA Academia 2014 Award), and the FEDER fund (UNGI10-4E-801)Wiley-VCH VerlagMinisterio de Economía y Competitividad (Espanya)info2019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionpeer-reviewed9 p.application/pdfhttp://hdl.handle.net/10256/16653http://hdl.handle.net/10256/16653© ChemPlusChem, 2019, vol. 14, núm. 10, p. 1870-1878Articles publicats (D-Q)Yadav, Sangeeta El Bakouri, Ouissam Jorner, Kjell Tong, Hui Dahlstrand, Christian Solà i Puig, Miquel Ottosson, Henrik 2019 Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds ChemPlusChem 14 10 1870 1878reponame: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/asia.201801821info:eu-repo/semantics/altIdentifier/issn/2192-6506info: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:10256/166532026-05-29T05:05:01Z
dc.title.none.fl_str_mv Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds
title Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds
spellingShingle Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds
Yadav, Sangeeta
Aromaticitat (Química)
Aromaticity (Chemistry)
Química quàntica
Quantum chemistry
title_short Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds
title_full Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds
title_fullStr Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds
title_full_unstemmed Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds
title_sort Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds
dc.creator.none.fl_str_mv Yadav, Sangeeta
El Bakouri, Ouissam
Jorner, Kjell
Tong, Hui
Dahlstrand, Christian
Solà i Puig, Miquel
Ottosson, Henrik
author Yadav, Sangeeta
author_facet Yadav, Sangeeta
El Bakouri, Ouissam
Jorner, Kjell
Tong, Hui
Dahlstrand, Christian
Solà i Puig, Miquel
Ottosson, Henrik
author_role author
author2 El Bakouri, Ouissam
Jorner, Kjell
Tong, Hui
Dahlstrand, Christian
Solà i Puig, Miquel
Ottosson, Henrik
author2_role author
author
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)
Química quàntica
Quantum chemistry
topic Aromaticitat (Química)
Aromaticity (Chemistry)
Química quàntica
Quantum chemistry
description Due to the reversal in electron counts for aromaticity and antiaromaticity in the closed-shell singlet state (normally ground state, S0) and lowest * triplet state (T1 or T0), as given by Hückel's and Baird's rules, respectively, fulvenes are influenced by their substituents in the opposite manner in the T1 and S0 states. This effect is caused by a reversal in the dipole moment when going from S0 to T1 as fulvenes adapt to the difference in electron counts for aromaticity in various states; they are aromatic chameleons. Thus, a substituent pattern that enhances (reduces) fulvene aromaticity in S0 reduces (enhances) aromaticity in T1, allowing for rationalizations of the triplet state energies (ET) of substituted fulvenes. Through quantum chemical calculations we now assess which substituents and which positions on the pentafulvene core are the most powerful for designing compounds with low or inverted ET. As a means to increase the -electron withdrawing capacity of cyano groups we found that protonation at the cyano N atoms of 6,6-dicyanopentafulvenes can be a route to on-demand formation of a fulvenium dication with a triplet ground state (T0). The five-membered ring of this species is markedly Baird-aromatic, although less than the cyclopentadienyl cation known to have a Baird-aromatic T0 state
publishDate 2019
dc.date.none.fl_str_mv 2019
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/10256/16653
http://hdl.handle.net/10256/16653
url http://hdl.handle.net/10256/16653
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/asia.201801821
info:eu-repo/semantics/altIdentifier/issn/2192-6506
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 Wiley-VCH Verlag
publisher.none.fl_str_mv Wiley-VCH Verlag
dc.source.none.fl_str_mv © ChemPlusChem, 2019, vol. 14, núm. 10, p. 1870-1878
Articles publicats (D-Q)
Yadav, Sangeeta El Bakouri, Ouissam Jorner, Kjell Tong, Hui Dahlstrand, Christian Solà i Puig, Miquel Ottosson, Henrik 2019 Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Triplet Ground State Compounds ChemPlusChem 14 10 1870 1878
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_ 1869413696929792000
score 15,812429

Similares en LA Referencia