Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes
dc.contributor.author
dc.date.accessioned
2015-05-11T10:44:43Z
dc.date.available
2015-05-11T10:44:43Z
dc.date.issued
2014
dc.identifier.issn
0002-7863
dc.identifier.uri
dc.description.abstract
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
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application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ja505240e
dc.relation.ispartof
© Journal of the American Chemical Society, 2014, vol. 136, núm. 30, p. 10743-10751
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Articles publicats (D-Q)
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Tots els drets reservats
dc.title
Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/630978/EU/Computational Exploration of Directed Evolution rules for tuning enzymatic activities/DIREVENZYME
info:eu-repo/grantAgreement/EC/FP7/252856/EU/Enzyme Design of Medical Interest/MEDENZYMEDESIGN
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
022142
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-5126