KOPS - The Institutional Repository of the University of Konstanz

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

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

Cite This

Files in this item

Files Size Format View

There are no files associated with this item.

CAO, Yang, Yong LIANG, Lei ZHANG, Sílvia OSUNA, Andra-Lisa M. HOYT, Alejandro L. BRISENO, K. N. HOUK, 2014. Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes. In: Journal of the American Chemical Society. American Chemical Society. 136(30), pp. 10743-10751. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja505240e

@article{Cao2014-07-30biste-52297, title={Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes}, year={2014}, doi={10.1021/ja505240e}, number={30}, volume={136}, issn={0002-7863}, journal={Journal of the American Chemical Society}, pages={10743--10751}, author={Cao, Yang and Liang, Yong and Zhang, Lei and Osuna, Sílvia and Hoyt, Andra-Lisa M. and Briseno, Alejandro L. and Houk, K. N.} }

<rdf:RDF xmlns:dcterms="http://purl.org/dc/terms/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#" xmlns:foaf="http://xmlns.com/foaf/0.1/" xmlns:void="http://rdfs.org/ns/void#" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/52297"> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/> <dcterms:issued>2014-07-30</dcterms:issued> <dcterms:abstract xml:lang="eng">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.</dcterms:abstract> <dc:creator>Houk, K. N.</dc:creator> <dc:creator>Briseno, Alejandro L.</dc:creator> <dc:creator>Liang, Yong</dc:creator> <dc:creator>Osuna, Sílvia</dc:creator> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2021-01-05T14:05:27Z</dcterms:available> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dc:contributor>Cao, Yang</dc:contributor> <dc:contributor>Hoyt, Andra-Lisa M.</dc:contributor> <dc:rights>terms-of-use</dc:rights> <dc:contributor>Briseno, Alejandro L.</dc:contributor> <dc:creator>Cao, Yang</dc:creator> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <bibo:uri rdf:resource="https://kops.uni-konstanz.de/handle/123456789/52297"/> <dc:language>eng</dc:language> <dcterms:title>Why bistetracenes are much less reactive than pentacenes in Diels-Alder reactions with fullerenes</dcterms:title> <dc:contributor>Liang, Yong</dc:contributor> <dc:contributor>Zhang, Lei</dc:contributor> <dc:contributor>Houk, K. N.</dc:contributor> <dc:creator>Hoyt, Andra-Lisa M.</dc:creator> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2021-01-05T14:05:27Z</dc:date> <dc:creator>Zhang, Lei</dc:creator> <dc:contributor>Osuna, Sílvia</dc:contributor> </rdf:Description> </rdf:RDF>

This item appears in the following Collection(s)

Search KOPS


Browse

My Account