Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes

The Diels-Alder (DA) reactions of pentacene (PT), 6,13-bis(2-trimethylsilylethynyl)pentacene (TMS-PT), bistetracene (BT), and 8,17-bis(2-trimethylsilylethynyl)bistetracene (TMS-BT) with the [6,6] double bond of [60]fullerene have been investigated by density functional theory calculations. Reaction...

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Detalhes bibliográficos
Autores: Cao, Yang, Liang, Yong, Zhang, Lei, Houk, Kendall N., Osuna Oliveras, Sílvia, Hoyt, Andra Lisa M., Briseño, Alejandro L.
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2014
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:10256/10362
Acesso em linha:http://hdl.handle.net/10256/10362
Access Level:Acesso embargado
Palavra-chave:Diels-Alder, Reacció de
Diels-Alder reaction
Fullerenes
Ful·lerens
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spelling Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenesCao, YangLiang, YongZhang, LeiHouk, Kendall N.Osuna Oliveras, SílviaHoyt, Andra Lisa M.Briseño, Alejandro L.Diels-Alder, Reacció deDiels-Alder reactionFullerenesFul·lerensThe Diels-Alder (DA) reactions of pentacene (PT), 6,13-bis(2-trimethylsilylethynyl)pentacene (TMS-PT), bistetracene (BT), and 8,17-bis(2-trimethylsilylethynyl)bistetracene (TMS-BT) with the [6,6] double bond of [60]fullerene have been investigated by density functional theory calculations. Reaction barriers and free energies have been obtained to assess the effects of frameworks and substituent groups on the DA reactivity and product stability. Calculations indicate that TMS-BT is about 5 orders of magnitude less reactive than TMS-PT in the reactions with [60]fullerene. This accounts for the observed much higher stability of TIPS-BT than TIPS-PT when mixed with PCBM. Surprisingly, calculations predict that the bulky silylethynyl substituents of TMS-PT and TMS-BT have only a small influence on reaction barriers. However, the silylethynyl substituents significantly destabilize the corresponding products due to steric repulsions in the adducts. This is confirmed by experimental results here. Architectures of the polycyclic aromatic hydrocarbons (PAHs) play a crucial role in determining both the DA barrier and the adduct stability. The reactivities of different sites in various PAHs are related to the loss of aromaticity, which can be predicted using the simple Hückel molecular orbital localization energy calculationsAmerican Chemical Society (ACS)infoinfo2014info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10256/10362http://hdl.handle.net/10256/10362© Journal of the American Chemical Society, 2014, vol. 136, núm. 30, p. 10743-10751Articles 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/10.1021/ja505240einfo:eu-repo/semantics/altIdentifier/issn/0002-7863info:eu-repo/semantics/altIdentifier/eissn/1520-5126info:eu-repo/grantAgreement/EC/FP7/630978info:eu-repo/grantAgreement/EC/FP7/252856Tots els drets reservatsinfo:eu-repo/semantics/embargoedAccessoai:recercat.cat:10256/103622026-05-29T05:05:01Z
dc.title.none.fl_str_mv Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes
title Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes
spellingShingle Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes
Cao, Yang
Diels-Alder, Reacció de
Diels-Alder reaction
Fullerenes
Ful·lerens
title_short Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes
title_full Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes
title_fullStr Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes
title_full_unstemmed Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes
title_sort Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes
dc.creator.none.fl_str_mv Cao, Yang
Liang, Yong
Zhang, Lei
Houk, Kendall N.
Osuna Oliveras, Sílvia
Hoyt, Andra Lisa M.
Briseño, Alejandro L.
author Cao, Yang
author_facet Cao, Yang
Liang, Yong
Zhang, Lei
Houk, Kendall N.
Osuna Oliveras, Sílvia
Hoyt, Andra Lisa M.
Briseño, Alejandro L.
author_role author
author2 Liang, Yong
Zhang, Lei
Houk, Kendall N.
Osuna Oliveras, Sílvia
Hoyt, Andra Lisa M.
Briseño, Alejandro L.
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Diels-Alder, Reacció de
Diels-Alder reaction
Fullerenes
Ful·lerens
topic Diels-Alder, Reacció de
Diels-Alder reaction
Fullerenes
Ful·lerens
description The Diels-Alder (DA) reactions of pentacene (PT), 6,13-bis(2-trimethylsilylethynyl)pentacene (TMS-PT), bistetracene (BT), and 8,17-bis(2-trimethylsilylethynyl)bistetracene (TMS-BT) with the [6,6] double bond of [60]fullerene have been investigated by density functional theory calculations. Reaction barriers and free energies have been obtained to assess the effects of frameworks and substituent groups on the DA reactivity and product stability. Calculations indicate that TMS-BT is about 5 orders of magnitude less reactive than TMS-PT in the reactions with [60]fullerene. This accounts for the observed much higher stability of TIPS-BT than TIPS-PT when mixed with PCBM. Surprisingly, calculations predict that the bulky silylethynyl substituents of TMS-PT and TMS-BT have only a small influence on reaction barriers. However, the silylethynyl substituents significantly destabilize the corresponding products due to steric repulsions in the adducts. This is confirmed by experimental results here. Architectures of the polycyclic aromatic hydrocarbons (PAHs) play a crucial role in determining both the DA barrier and the adduct stability. The reactivities of different sites in various PAHs are related to the loss of aromaticity, which can be predicted using the simple Hückel molecular orbital localization energy calculations
publishDate 2014
dc.date.none.fl_str_mv 2014
info
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/10362
http://hdl.handle.net/10256/10362
url http://hdl.handle.net/10256/10362
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/ja505240e
info:eu-repo/semantics/altIdentifier/issn/0002-7863
info:eu-repo/semantics/altIdentifier/eissn/1520-5126
info:eu-repo/grantAgreement/EC/FP7/630978
info:eu-repo/grantAgreement/EC/FP7/252856
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/embargoedAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv embargoedAccess
dc.format.none.fl_str_mv 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 the American Chemical Society, 2014, vol. 136, núm. 30, p. 10743-10751
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
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score 15,812455

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