Do [all]-S,S'-Dioxide Oligothiophenes Show Electronic and Optical Properties of Oligoenes and/or of Oligothiophenes?
A comprehensive photophysical and spectroscopic (electronic and Raman) study guided by density functional theory, DFT, CIS, and correlated ab initio calculations has been performed on a series of fully oxidized oligothiophenes with variable chain length, and up to four rings. A comparison with the p...
| Publicado en: | Journal of the American Chemical Society Vol. 132; no. 17; pp. 6231 - 6243 |
|---|---|
| Autores principales: | , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
5/5/2010
|
| 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=50730878&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 50730878 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: 5/5/2010 vid: 132 iid: 17 pid: 997 pub: American Chemical Society artinfo: ui: 50730878 10.1021/ja101015q ppf: 6231 ppct: 12 formats: tig: atl: Do [all]-S,S'-Dioxide Oligothiophenes Show Electronic and Optical Properties of Oligoenes and/or of Oligothiophenes? aug: au: Oliva, María Moreno Casado, Juan López Navarrete, Juan T. Patchkovskii, Serguei Goodson III, Theodore Harpham, Michael R. Seixas de Melo, J. Sérgio Amir, Elizabeta Rozen, Shlomo affil: Department of Physical Chemistry, University of Málaga, Campus de Teatinos s/n, Málaga 29071, Spain Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, K1A 0R6 Canada Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109 Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978, Israel su: Thiophenes Electrons Optical properties Photoemission Density functionals sug: subj: Thiophenes Electrons Optical properties Photoemission Density functionals ab: A comprehensive photophysical and spectroscopic (electronic and Raman) study guided by density functional theory, DFT, CIS, and correlated ab initio calculations has been performed on a series of fully oxidized oligothiophenes with variable chain length, and up to four rings. A comparison with the properties of oligoenes and oligothiophenes is proposed. Absorption, fluorescence, lifetimes, flash-photolysis, phosphorescence, two-photon absorption, Raman, resonance Raman, and thermospectroscopy data are collected and interpreted according to the obtained theoretical results. The interest is focused on the ground electronic state and in the low-lying excited electronic states. Full oxygenation of the sulfur atoms of oligothiophenes results in: (i) restricted inter-ring isomerization such as observed from the absorption spectra; (ii) an effective quenching of fluorescence, and (iii) the appearance of dual emission. The emission features are explained by the interference of a dipole-allowed and a dipole-forbidden singlet excited states leading to simultaneous lighting from a local Frankel and an intramolecular charge transfer photon-releasing configurations. These two excited states contribute to the broadening of the light emission spectrum. These properties highlight the similarity of these samples to that of oligoenes with comparable number of π-electrons. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
|---|