Photo-induced reorientational behavior of films of a liquid crystalline polymer with azobenzene side chains was studied by means of UV-Vis absorption spectroscopy and Fourier transform infrared transmission and reflection-absorption spectroscopy. The incident directions of light for photoisomerization played a critical role in the photocontrol of out-of-plane (three-dimensional) orientation of the azobenzenes in films. Tilted directions of the azobenzene residues were evaluated by using polarized UV-Vis absorption spectra. Photoreoriented states of azobenzene chromophores including photodichroism and tilted alignment were enhanced by successive annealing of photoirradiated films at temperatures close to the glass transition temperature of the polymer.
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