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Study of Molecular Dynamics in Poly(n-alkyl methacrylates) by Light Induced Absorption Anisotropy

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    Study of Molecular Dynamics in Poly(n-alkyl methacrylates) by Light Induced Absorption Anisotropy
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    Institute of Chemical Kinetics and Combustion, Novosibirsk, 630090, Russian Federation
    *E-mail: [email protected]
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    The Journal of Physical Chemistry B

    Cite this: J. Phys. Chem. B 2014, 118, 32, 9800–9807
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    https://doi.org/10.1021/jp504276y
    Published July 28, 2014
    Copyright © 2014 American Chemical Society
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    Abstract

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    Formation of absorbance anisotropy under linearly polarized irradiation at 405 nm in films of poly(ethyl methacrylate) (PEMA), poly(n-butyl methacrylate) (PnBMA), and poly(n-hexyl methacrylate) (PnHexMA) doped with azo compound has been studied in a wide temperature range below Tg. The anisotropy formation kinetics has been well described under the assumption that there are two types of environments in the polymer matrixes: mobile and immobile. The mobile environment allows the dopant to reorient in the course of cis–trans–cis isomerization cycle and the immobile environment does not. The fraction of mobile environments was estimated to be 0.12 in PEMA, 0.65 in PnBMA, and 1.0 in PnHexMA. An increase in the fraction of mobile environments within the series PEMA–PnBMA–PnHexMA have been associated with an increase in the size of alkyl nanodomains. The average angle of transition dipole rotation upon isomerization and the amplitude of molecules librations have been estimated in the temperature range studied.

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    Supporting Information

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    Note regarding the kinetics of photoisomerization. Figure S1: The kinetics of photoisomerization in the case of strong light absorption. Figure S2: Time profiles of absorbances (AbsY and AbsZ) of NAMB in PnHexMA in the course of irradiation with linearly polarized light of 405 nm at 193 K. Figure S3: The example of fitting of the absorbance and anisotropy time profiles. Figure S4: Dependence of the steady-state anisotropy on cis isomer fraction for the case of nonrotating molecules. This material is available free of charge via the Internet at http://pubs.acs.org/.

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    Cited By

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    This article is cited by 4 publications.

    1. Sergey Grebenkin and Arkadiy B. Meshalkin . Wavelength Dependence of the Reorientation Efficiency of Azo Dyes in Polymer Matrixes. The Journal of Physical Chemistry B 2017, 121 (35) , 8377-8384. https://doi.org/10.1021/acs.jpcb.7b03171
    2. S. Grebenkin, V. M. Syutkin. Isomerization and reorientation of Disperse Red 1 in poly(ethyl methacrylate). The Journal of Chemical Physics 2021, 155 (16) https://doi.org/10.1063/5.0063031
    3. Alexey Bobrovsky, Valery Shibaev, Alexey Piryazev, Denis V. Anokhin, Dimitri A. Ivanov, Olga Sinitsyna, Vera Hamplova, Miroslav Kaspar, Alexej Bubnov. Photo-Orientation Phenomena in Photochromic Liquid Crystalline Azobenzene-Containing Polymethacrylates with Different Spacer Length. Macromolecular Chemistry and Physics 2017, 218 (16) , 1700127. https://doi.org/10.1002/macp.201700127
    4. S.Yu. Grebenkin, V.M. Syutkin, Denis S. Baranov. Mutual orientation of the n → π * and π → π * transition dipole moments in azo compounds: Determination by light-induced optical anisotropy. Journal of Photochemistry and Photobiology A: Chemistry 2017, 344 , 1-7. https://doi.org/10.1016/j.jphotochem.2017.04.031
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    The Journal of Physical Chemistry B

    Cite this: J. Phys. Chem. B 2014, 118, 32, 9800–9807
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp504276y
    Published July 28, 2014
    Copyright © 2014 American Chemical Society
    Request reuse permissions

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