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Rotamer-Specific Photoisomerization of Difluorostilbenes from Transient Absorption and Transient Raman Spectroscopy.
Quick, M; Dobryakov, A L; Ioffe, I N; Berndt, F; Mahrwald, R; Ernsting, N P; Kovalenko, S A.
Afiliación
  • Quick M; Department of Chemistry, Humboldt-Universität zu Berlin , Brook-Taylor-Str. 2, D-12489 Berlin, Germany.
  • Dobryakov AL; Department of Chemistry, Humboldt-Universität zu Berlin , Brook-Taylor-Str. 2, D-12489 Berlin, Germany.
  • Ioffe IN; Department of Chemistry, Lomonosov Moscow State University , Moscow, Russia.
  • Berndt F; Department of Chemistry, Humboldt-Universität zu Berlin , Brook-Taylor-Str. 2, D-12489 Berlin, Germany.
  • Mahrwald R; Department of Chemistry, Humboldt-Universität zu Berlin , Brook-Taylor-Str. 2, D-12489 Berlin, Germany.
  • Ernsting NP; Department of Chemistry, Humboldt-Universität zu Berlin , Brook-Taylor-Str. 2, D-12489 Berlin, Germany.
  • Kovalenko SA; Department of Chemistry, Humboldt-Universität zu Berlin , Brook-Taylor-Str. 2, D-12489 Berlin, Germany.
J Phys Chem B ; 122(3): 1049-1059, 2018 01 25.
Article en En | MEDLINE | ID: mdl-29178802
Photoisomerization of 2,2'-, 3,3'-, and 4,4'-difluorostilbene (F2, F3, F4, respectively) in n-hexane, perfluoro-n-hexane, and acetonitrile is studied with broadband transient absorption (TA) and femtosecond stimulated Raman (FSR) spectroscopy and by DFT/TDDFT calculations. F2 and F3 possess three rotamers (rotational isomers) each, while F4 has one single conformation only. These differences are reflected in TA and FSR spectra. Thus F4 reveals a monoexponential decay of TA with τ1 = 172 ps in n-hexane, as expected for a single species. For F2 and F3, the decays are biexponential in all solvents, corresponding to two distinctly discerned rotamers or rotamer fractions. Specifically, for F2 in n-hexane, τ1 = 357 ps (83%) and τ2 = 62 ps (17%), and for F3 in the same solvent, τ1 = 222 ps (57%), and τ2 = 81 ps (43%). The weights in brackets agree with theoretically estimated ground-state abundances of the rotamers. Furthermore, a global fit of the TA and FSR data allows us to extract the spectra of the pure rotamers. The Raman spectra of S0 and S1 are in qualitative agreement with calculations.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Tipo de estudio: Qualitative_research Idioma: En Revista: J Phys Chem B Asunto de la revista: QUIMICA Año: 2018 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Estados Unidos
Texto completo
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Imprimir
XML
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Tipo de estudio: Qualitative_research Idioma: En Revista: J Phys Chem B Asunto de la revista: QUIMICA Año: 2018 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Estados Unidos