Controlling the Diradical Character of Thiele Like Compounds

Organic diradicals play an important role in many fields of chemistry, biochemistry, and materials science. In this work, by means of high-level theoretical calculations, we have investigated the effect of representative chemical substituents in p-quinodimethane (pQDM) and Thiele's hydrocarbons...

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Detalles Bibliográficos
Autores: Anglada Rull, Josep M., Poater, Jordi, Moreira, Ibério de P. R., Bofill, Josep Maria
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/331653
Acceso en línea:http://hdl.handle.net/10261/331653
https://api.elsevier.com/content/abstract/scopus_id/85164441639
Access Level:acceso abierto
Palabra clave:Organic diradicals
p-quinodimethane (pQDM)
Thiele’s hydrocarbons
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
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spelling Controlling the Diradical Character of Thiele Like CompoundsAnglada Rull, Josep M.Poater, JordiMoreira, Ibério de P. R.Bofill, Josep MariaOrganic diradicalsp-quinodimethane (pQDM)Thiele’s hydrocarbonshttp://metadata.un.org/sdg/3Ensure healthy lives and promote well-being for all at all agesOrganic diradicals play an important role in many fields of chemistry, biochemistry, and materials science. In this work, by means of high-level theoretical calculations, we have investigated the effect of representative chemical substituents in p-quinodimethane (pQDM) and Thiele's hydrocarbons with respect to the singlet-triplet energy gap, a feature characterizing their diradical character. We show how the nature of the substituents has a very important effect in controlling the singlet-triplet energy gap so that several compounds show diradical features in their ground electronic state. Importantly, steric effects appear to play the most determinant role for pQDM analogues, with minor effects of the substituents in the central ring. For Thiele like compounds, we found that electron-withdrawing groups in the central ring favor the quinoidal form with a low or almost null diradical character, whereas electron-donating group substituents favor the aromatic-diradical form if the electron donation does not exceed 6-π electrons. In this case, if there is an excess of electron donation, the diradical character is reduced. The electronic spectrum of these compounds is also calculated, and we predict that the most intense bands occur in the visible region, although in some cases characteristic electronic transition in the near-IR region may appear.The authors thank the financial support from the Spanish Ministerio de Economía y Competitividad (project nos. PID2019-109518GB-I00 and PID2019-106830GB-I00 and Spanish Structures of Excellence María de Maeztu program, through grant nos. MDM-2017-0767 and CEX2021-001202-M); the Catalan Government (project nos. 2021SGR354 and 2021SGR442); and Consorci de Serveis Universitaris de Catalunya (CSUC) for providing computational resources.Peer reviewedAmerican Chemical Society0000-0003-4526-36240000-0002-0814-50740000-0002-2684-69820000-0002-0974-4618Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202320232023info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/331653https://api.elsevier.com/content/abstract/scopus_id/85164441639reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)InglésThe Journal of organic chemistryhttps://doi.org/10.1021/acs.joc.3c00482Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3316532026-05-22T06:33:51Z
dc.title.none.fl_str_mv Controlling the Diradical Character of Thiele Like Compounds
title Controlling the Diradical Character of Thiele Like Compounds
spellingShingle Controlling the Diradical Character of Thiele Like Compounds
Anglada Rull, Josep M.
Organic diradicals
p-quinodimethane (pQDM)
Thiele’s hydrocarbons
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
title_short Controlling the Diradical Character of Thiele Like Compounds
title_full Controlling the Diradical Character of Thiele Like Compounds
title_fullStr Controlling the Diradical Character of Thiele Like Compounds
title_full_unstemmed Controlling the Diradical Character of Thiele Like Compounds
title_sort Controlling the Diradical Character of Thiele Like Compounds
dc.creator.none.fl_str_mv Anglada Rull, Josep M.
Poater, Jordi
Moreira, Ibério de P. R.
Bofill, Josep Maria
author Anglada Rull, Josep M.
author_facet Anglada Rull, Josep M.
Poater, Jordi
Moreira, Ibério de P. R.
Bofill, Josep Maria
author_role author
author2 Poater, Jordi
Moreira, Ibério de P. R.
Bofill, Josep Maria
author2_role author
author
author
dc.contributor.none.fl_str_mv 0000-0003-4526-3624
0000-0002-0814-5074
0000-0002-2684-6982
0000-0002-0974-4618
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Organic diradicals
p-quinodimethane (pQDM)
Thiele’s hydrocarbons
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
topic Organic diradicals
p-quinodimethane (pQDM)
Thiele’s hydrocarbons
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
description Organic diradicals play an important role in many fields of chemistry, biochemistry, and materials science. In this work, by means of high-level theoretical calculations, we have investigated the effect of representative chemical substituents in p-quinodimethane (pQDM) and Thiele's hydrocarbons with respect to the singlet-triplet energy gap, a feature characterizing their diradical character. We show how the nature of the substituents has a very important effect in controlling the singlet-triplet energy gap so that several compounds show diradical features in their ground electronic state. Importantly, steric effects appear to play the most determinant role for pQDM analogues, with minor effects of the substituents in the central ring. For Thiele like compounds, we found that electron-withdrawing groups in the central ring favor the quinoidal form with a low or almost null diradical character, whereas electron-donating group substituents favor the aromatic-diradical form if the electron donation does not exceed 6-π electrons. In this case, if there is an excess of electron donation, the diradical character is reduced. The electronic spectrum of these compounds is also calculated, and we predict that the most intense bands occur in the visible region, although in some cases characteristic electronic transition in the near-IR region may appear.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023
2023
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/10261/331653
https://api.elsevier.com/content/abstract/scopus_id/85164441639
url http://hdl.handle.net/10261/331653
https://api.elsevier.com/content/abstract/scopus_id/85164441639
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv The Journal of organic chemistry
https://doi.org/10.1021/acs.joc.3c00482
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,81155

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