Excited State s-cis Rotamers Produced by Extreme Red Edge Excitation of all-trans-1,4-Diphenyl-1,3-butadiene

Stacie E. Wallace-Williams, Søren Møller, Robert A. Goldbeck, Kerry M. Hanson, James W. Lewis, W. Atom Yee, David S. Kliger

    Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review


    The shapes of the fluorescence emission and lowest excited singlet-state absorption spectra of all-trans-1,4- diphenylbutadiene (DPB) in hydrocarbon solvents vary with excitation wavelength when exciting on the extreme red edge of the ground-state absorption spectrum. This contrasts with the wavelength independence observed for the excited singlet-state absorption and fluorescence emission spectra of 1,5-diphenyl-2,3,4,6,7,8- hexahydronaphthalene and for the fluorescence emission spectra of 1,4diphenyl-1,3-cyclopentadiene, s-trans and s-cis structural analogs of DPB, respectively. The spectral changes in DPB can be explained in terms of an excitation wavelength-dependent production of s-cis and s-trans rotamer populations in the excited state. The DPB fluorescence emission spectrum was resolved into s-cis and s-trans components. The vibronic structure of the s-cis fluorescence spectrum is similar to that of s-trans, but the band origin is red-shifted and there is a slightly larger amplitude on the red edge. The excited-state absorption spectrum of s-cis DPB appears to be red-shifted relative to that of s-trans DPB as well.
    TidsskriftJournal of Physical Chemistry
    Udgave nummer38
    Sider (fra-til)9587-9592
    StatusUdgivet - 1993

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