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Orthogonal polarization component Fit to the orthogonal polarization component Intensities of probe beam (V)
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0.0 Irradiation 0 10 20 30 Time (min) 40 50
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Intensity of the transmitted probe beam(a.u.) 1.4 Intensities of probe beam (V) 1.3 1.2 1.1 0.2 0.1 0.0 Irradiation 140 145 Time (min) State 1 State 2 State 1 State 2 State 1 State 2 State 1 (b) 150
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Figure 2.9. Optical anisotropy induced by the light in a lm of the compound Alizarin Yellow GG-PEI: kinetics of the parallel (dashed black line) and orthogonal (solid gray line) polarization components of the transmitted probe beam. (a) Induction and relaxation, solid black line presents two-exponential decay t to the data, and (b) switching by alternation of polarization of the irradiating beam. Source: Kulikovska et al., 2007. Reproduced with permission from American Chemical Society.
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Figure 2.10. Chemical structure of complexes of poly(vinyl-N-alkylpyridinium) with Methyl Orange and the Ethyl Orange (EO) with C12D and C16D surfactants.
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The maximum value of photoinduced birefringence achieved were 0.067 and 0.31 for ethyl- and methyl-quaternized polyvinylpyridine (see Fig. 2.10a), respectively (Zhang et al., 2008; Xiao et al., 2007). The authors believe that such a great difference in photoorientation properties is hardly attributed to structural difference consisting of one methylene group, but more probably to the difference in synthesis, puri cation, lm preparation, etc. A rather simple approach for design of low-molecular-weight ionic supramolecular complexes has been recently proposed (Zakrevskyy et al., 2005, 2004; Guan et al., 2003). These new materials are formed by introduction of oppositely charged ions between different low molecular tectonic units and are called ISA complexes. In contrast to the discussed LbL and polyelectrolyte-based ionic complexes, the polymer unit is usually replaced by low-molecular-weight surfactant. Application of the ISA concept to produce photosensitive low-molecularweight materials with good lm-forming properties, which are capable of undergoing light-induced generation of optical anisotropy, has been proved to be very successful (Zakrevskyy et al., 2006a). The photosensitive ISA complexes consist of charged azobenzene-containing photosensitive units complexed with oppositely charged surfactants. The chemical structure of the most detailed investigated complexes is shown in Fig. 2.10b. Other examples of the photosensitive complexes can be found in a study by Zakrevskyy et al. (2006b). It should be noted that proper design of ISA complexes, based on functionalized tectonic units and surfactants, results in a new strategy for creation of functionalized liquid crystals. This approach can lead to speci c optical functions of the material. Induction of optical anisotropy in spin-coated lm of the ISA complexes under irradiation with polarized light of an Ar+ laser was very effective (Zakrevskyy et al., 2007). Dichroic ratios of 50 for the EO C12D complex and of 20 for the EO C16D complex have been obtained (Fig. 2.12a and b). To the best of the authors knowledge, this is the highest value of photoinduced anisotropy. It was shown that both complexes exist in highly ordered columnar LC phases at room temperature, and their photobehavior is strongly affected by their liquid crystallinity. Spin-coated lms of the complexes are built from LC domains. The photoalignment of the complexes depends strongly on the size of the domains. In the case of small domains, the photoalignment is the most effective. Photoreorientation in the complexes is not local like in azobenzene-containing polymers, but is a cooperative process and connected to mechanical rotation of domains.
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Figure 2.11. Photoinduced birefringence (PIB) in a spin-coated lm (200-nm thick) of the MO/poly(vinyl-N-methylpyridinium) complex. PIB curves (a) (A, write ON 10 s; B, write OFF 30 s; C, erasure ON) taken at the same spot after different thermal treatment. (b) Multiple write-erase cycles (251C; write ON 10 s, write OFF 30 s, erase ON 30 s, erase OFF 10 s; only the rst ve of eight identical cycles are shown. Source: Zhang et al., 2008. Reprinted with permission from American Chemical Society.
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Domains in the initial lm are aligned in such a way that columns of the complex are parallel to the substrate with isotropic orientational distribution parallel to the lm plane. During irradiation, there is an in-plane reorientation of domains (columns).
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