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Figure 10.14. HTP as a function of L/D of chiral azobenzene compounds.
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o-, m-, p-azo-7), and Gr-C (o-, m-, p-azo-8, o-, m-, p-azo-9). Compounds with a single chiral group in azobenzene core moiety fall in Gr-A and Gr-B. Compounds in Gr-B have higher HTPtrans as well as higher D(HTP) compared with the compounds in Gr-A. One of the reasons of the difference in D(HTP) of the chiral azobenzene compounds may be the molecular size of the chiral groups. Azo-10 with cholesterol group as chiral moiety showed much smaller D(HTP), although its D(L/D) was comparable to others. Figure 10.11 shows models of isomers of azo-6 and azo-10. As can be seen in the gure, the trans forms are rodlike, whereas the cis forms possess a bent structure. Comparison of the models revealed that the size of the bent part of azo-10 is much larger than that of azo-6, because of large molecular size of the cholesterol group. Therefore, it can be assumed that the cis form of azo-10 can interact with nematogenic neighbors more ef ciently than azo6 and other azobenzene compounds having smaller chiral groups. Consequently, no signi cant difference between HTPtrans and HTPcis of azo-10 was observed. However, compounds in Gr-C showed higher HTP and D(HTP) as given in Table 10.3 and Fig. 10.14. The introduction and isomerization of plural photochromic groups in a single chiral core is favorable for effective modulation of the helical structure photochemically. The zigzag molecular shape of the compounds in Gr-C contributed to the larger photochemical change in HTP. However, o-azo9 showed a little deviation from the plot of Gr-C. Figure 10.15 shows the models
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Figure 10.15. Optimized structures for o-azo-9 by MOPAC at PM3 level.
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of isomers of o-azo-9. A zigzag shape of trans-o-azo-9 contributes to its smaller HTP. In addition, the linearity of core part ( N=N Ar COO ) of cis-o-azo-9 is extremely lower than that of m-azo-9 and other rod-shaped molecules, because of bonding at ortho position. Consequently, o-azo-9 exhibits smaller HTP as well as smaller D(HTP) compared with others. The results suggest that D(HTP) of the chiral photochromic compounds is related not only to the aspect ratio but also to the features of the chiral groups such as size, compactness, rigidity, linearity, planarity, and so on.
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It is well known that a Ch LC shows three major textures depending on applied electric eld and surface alignment properties, when it is sandwiched between two parallel glass plates; they are planar texture, focal conic texture, and homeotropic texture as shown in Fig. 10.16 (Demus and Richter, 1978). In the planar texture, the Ch LCs re ect light selectively depending on the helical pitch. The Ch LCs in the focal conic texture scatter light in forward directions, because of its polydomain structure with the helical structure. The Ch LCs can exist in both planar texture and focal conic texture at zero eld condition (Yang et al., 1997). However, unwinding of helical structure of the Ch LC with an electric eld provides homeotropic structure, where the LC director is perpendicular to the cell surface. Consequently, the Ch LCs become transparent. If one can control the helical pitch as well as the textures of the Ch LC photochemically, the photoresponsive Ch LCs will be promising for various types of optical materials.
Planar texture
Focal conic texture
Homeotropic texture
E > EC
Light scattering
Figure 10.16. Schematic diagrams of optical properties of Ch LCs.
In addition, the Ch LCs in the planar texture can be regarded as a onedimensional photonic band gap material, because of their periodical helical structure. This unique property will open new possibilities for application of the Ch LCs such as tunable laser and so on (Matsuhisa et al., 2007; Belyakov, 2006; Lin et al., 2005; Funamoto et al., 2003; Furumi et al., 2003; Kopp et al., 2003, 1998; Shibaev et al., 2003; Matsui et al., 2002; Ozaki et al., 2002). This section discusses the photochemical switching of selective re ection, transparency, helical sense, and lasing through the phototuning of helical structure of the Ch LCs by photoisomerization of chiral azobenzene compounds.