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Typical applications include diffractive optical elements (Goldenberg et al, 2008a,b; Kulikovska et al, 2008; Natansohn and Rochon, 2002; Viswanathan et al, 1999), waveguide coupler (Choi et al, 2003; Kang et al, 2003; Barrett et al, 1997), lasing (Ye et al, 2007), and optical storage (Oliveira et al, 2005; Egami et al, 2000) Applications of nano- and microstructured surfaces as aligning layers (Kim et al, 2002; Dantsker et al, 2001), analysis of optical near eld (Fukuda et al, 2001a), templates (Kim et al, 2006a), nanodevice processing (Ohdaira et al, 2006), and biology (Barille et al, 2006; Baac et al, 2004) also attract more and more interest All applications discussed earlier just give a general idea about the photoinduced processes of azobenzene related to the topics of this chapter.

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For the sake of simplicity, the authors have kept away from the material questions Nevertheless, all discussed processes depend not only on the chromophore but are strongly affected by its surroundings and the macroscopic properties of the medium Especially, the stability of the induced changes is determined mostly by the embedding matrix Vice versa, the photoinduced motions of chromophore can modify its surroundings This interplay of light, light-sensitive moiety, and embedding matrix is the key for the understanding of the photoinduced orientation and mass transport It is also the key for design of any applicable material It is kept in mind as a leading idea by reviewing the results in this chapter Following consideration can help to relate different photoreactions of chromophore, in uence of the matrix and the observed photoinduced processes The authors view is outlined in Fig 21 Depending on the irradiation conditions,.

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the molecular photoreaction of azobenzene induces motions on a quite different length scale The photoexcitation involves the chromophore alone and correspondingly may be related to the scale of angstroms It may be used, for example, in nonlinear optics (NLO) The isomerization additionally involves the local surroundings of the chromophore on the nanometer scale and depends strongly, for example, on the free volume and intermolecular interactions Also, the orientation is a more or less local process on nanometer scale, which, in turn, can affect the orientational order of the neighboring molecular segments It is important if the induction of birefringence and, especially, its stability is considered On the contrary, the mass transport implies the translation of chromophore on a micrometer scale that necessarily produces a movement of the neighboring molecular segments or even of the whole molecules The intermolecular interactions are essential for this process.

But additionally, the matrix properties and morphology become of particular importance if the formation of SRG is considered Moreover, the stability of SRG is provided almost exclusively by the matrix Now, the azobenzene materials undergoing both effects should be discussed in more detail Photoorientation of azobenzenes takes place in solutions, liquid crystals, or glassy polymers; amount and stability of the induced anisotropy strongly depend on the dynamics of the matrix In contrast to photoorientation, light-induced mass transport was observed only in glassy systems With respect to this, both effects can take place in a variety of quite different photochromic matrices, which are schematically depicted in Fig 22 So far the main interest was focused on glassy polymers One should distinguish between azobenzene-doped polymers (Fig 22a) and azobenzene-functionalized polymers (Fig 2.

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