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...
| Publicado en: | Journal of the American Chemical Society Vol. 136; no. 30; pp. 10743 - 10752 |
|---|---|
| Autores principales: | , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
7/30/2014
|
| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=97861823&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 97861823 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 7/30/2014 vid: 136 iid: 30 pid: 997 pub: American Chemical Society artinfo: ui: 97861823 10.1021/ja505240e ppf: 10743 ppct: 9 formats: tig: atl: Why Bistetracenes Are Much Less Reactive Than Pentacenes in Diels–Alder Reactions with Fullerenes. aug: au: Yang Cao Yong Liang Lei Zhang Osuna, Sílvia Hoyt, Andra-Lisa M. Briseno, Alejandro L. Houk, K. N. affil: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States Department of Polymer Science & Engineering, Conte Polymer Research Center, University of Massachusetts, Amherst, Massachusetts 01003, United States su: Pentacene Diels-Alder reaction Fullerenes Double bonds Density functional theory Free energy (Thermodynamics) Substituents (Chemistry) Polycyclic aromatic hydrocarbons sug: subj: Pentacene Diels-Alder reaction Fullerenes Double bonds Density functional theory Free energy (Thermodynamics) Substituents (Chemistry) Polycyclic aromatic hydrocarbons ab: 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. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2014 holdings: @attributes: islocal: N |
|---|