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3.4.4.3. Photochemical Phase Transition of Azobenzene LC Polymers. LC polymers possess properties of both polymers and LCs and currently are regarded as promising photonic materials because of their advantageous properties mentioned earlier. Wendorff and coworkers reported the rst example of a photon-mode photoresponse in LC polymers, namely, holographic recording in LC polymer lms containing azobenzene moieties and mesogenic groups (Eich et al., 1987; Eich and Wendorff, 1987). Ikeda et al. (1990a,b, 1988) reported the rst example of the photochemical phase transition in LC polymers; they demonstrated that by irradiation of LC polymers doped with LMW azobenzene derivatives with UV light to cause trans cis isomerization led to a nematic isotropic phase transition; upon cis trans back-isomerization, the LC polymers reverted to the initial nematic phase. Although doping the chromophores in a matrix is most convenient, the resultant LC polymer systems often exhibit instabilities, such as phase separation and microcrystallization. This occurs because of the mobility of the azobenzene chromophores in the matrix and the propensity of the dipolar azobenzene units to form aggregates. Higher quality LC polymer systems are obtained when the azobenzene moiety is covalently bound to the host polymer matrix, and this approach is now preferable for most applications. These materials combine the stability and processability of LC polymers, with the unusual photoresponsive behavior of the azobenzene groups. A variety of

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LC copolymers were prepared, and their photochemical phase transition behavior was examined (Tsutsumi et al, 1998a; Sasaki et al, 1992; Ikeda et al, 1990b,c) One of the important factors of the photoresponsive LCs is their responses to optical stimuli In this respect, the response time of the photochemical phase transition has been explored by time-resolved measurements (Sasaki et al, 1992; Ikeda et al, 1991; Kurihara et al, 1990) Photochromic reactions are in general very fast, occurring on a timescale of picoseconds If an ultrafast laser with a pulse width on the picosecond scale is used as an excitation light source to induce phase transitions of LC systems containing photochromic molecules, photochemical reactions of the photochromic molecules can be completed in picoseconds, and the Tc of the system can be decreased below the irradiation temperature on this timescale.

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This means that immediately after pulse irradiation, a nonequilibrium state is produced, which is thermodynamically an isotropic phase in its equilibrium state but shows an anisotropy because orientational relaxation of mesogens is not completed The response of the whole LC systems depends strongly on this orientational relaxation of the mesogens, which in fact is the rate-determining step, especially in highly viscous LC polymers that require a relatively long time (Ikeda, 2003) A new system has been developed in which every mesogen in the LC or LC polymer is photosensitive (Ikeda, 2001; Tsutsumi et al, 1998b; Tsutsumi et al, 1997; Ikeda and Tsutsumi, 1995) For example, the azobenzene moiety could play roles as both a mesogen and a photosensitive moiety (Fig 320) in azobenzene derivatives that form LC phases.

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