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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of inorganic and organometallic polymers and materials 1 (1991), S. 3-35 
    ISSN: 1572-8870
    Keywords: Fluorescence ; polysilane ; σ conjugation ; conformation ; segment distribution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A comprehensive study of the electronic absorption and emission spectra and the fluorescence quantum yield and lifetime of seven poly(di-n-alkylsilane)s and of three isotopically labelled poly(di-n-hexylsilane)s in hydrocarbon solution at room temperature is reported. Also reported are fluorescence polarization and carbon tetrachloride quenching of fluorescence of poly(di-n-hexylsilane). The observed fluorescence spectra, quantum yield, and polarization depend on the selected excitation energy in a very characteristic fashion, whereas the fluorescence lifetime does not; however, it depends on the selected emission energy. These characteristic dependencies are qualitatively accounted for by the previously proposed segment distribution model if one assumes that the photophysical behavior at higher excitation energies is strongly affected by the presence of a low-lying weakly allowed state in short-segment chromophores and the behavior at lower excitation energies is dictated by the selective excitation of emitting long-segment chromophores.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1669-1677 
    ISSN: 0887-6266
    Keywords: photo-assisted poling ; polymer dynamics ; polymer structure ; nonlinear optical polyimides ; high glass transition temperature ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have used combinations of light, heat, and electrostatic fields to investigate the orientation of nonlinear azo-chromophores chemically incorporated into high glass transition temperature (Tg) polyimides. A number of nonlinear optical polyimides have been synthesized in which the interaction between the nonlinear optical chromophore and the polymer main chain was systematically altered to determine to what extent this steric interaction influences the orientation of the nonlinear chromophore. Chromophores in polymers may be oriented by a number of methods: (a) polarized light at room temperature (i.e., photo-induced orientation or PIO), (b) polarized light and electric fields (i.e., photo-assisted poling or PAP) at temperatures ranging from room temperature to the polymer Tg, and (c) electric fields at Tg (thermal poling). While thermal poling and PIO are usually possible, PAP depends strongly on the molecular structure of the polymer. Previously we have shown that PIO can be accomplished at room temperature in a system where the nonlinear chromophore is embedded into the polyimide main chain via the donor substituent, and this orientation can only be thermally erased at temperatures approaching Tg. In this article we show that, whereas photoisomerization can efficiently depole donor-embedded polyimides in a matter of few minutes at room temperature, PAP does not induce any polar order. This behavior is in marked contrast to a structurally related, side-chain, nonlinear polyimide, in which the azo chromophore is tethered via a flexible linkage to the polymer backbone. In this case some PAP occurs even at room temperature, while no PAP is observed for a donor-embedded system with a similar Tg. We suggest that the orientation during PAP below Tg in the side-chain polyimide is primarily due to the movement of the azo side chains, and there is a very little coupling of this motion to the main chain. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1669-1677, 1998
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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