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PVS, or PSS or rather exotic ones like chitosan, carragenan, cyclodextrine, or dendritic polyelectrolytes have been employed LbL layers with low-molecularweight azobenzene species could be considered as analogue of typical materials used for photoorientation and photoinduced mass transport, namely, azobenzene side-chain polymers In this case, covalent bonding of azobenzene moieties and polymer is replaced with ionic interactions (weak or strong depending on the type of polyelectolyte) (compare Fig 22b and d) The above-mentioned restriction to the structure of azodye is also of crucial importance to resulting photochemical properties Namely this causes a restriction on the freedom of movement of the azobenzene species, which seems to be of particular importance for the photoinduced mass transport Depending on the number of charged groups and polyelectrolyte type, these restrictions would be more or less pronounced Photoisomerization has been investigated for some of these solid-state complexes.

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As generally LbL procedure is rather tedious and time consuming (even using robotic technique available nowadays), from the practical viewpoint it would be attractive only in case of rather thin lms Figure 27 displays low molecular azobenzene derivatives, some of them commercially available, which were used to study photoinduced orientation Both negatively and positively charged dyes have been employed Relatively high dichroic ratio up to 23 due to geometry of the molecule (high aspect ratio of Direct Red 80) has been achieved (Advincula et al, 2003) To manufacture these lms with PDADMAC of ca 100-nm thickness, 100 layers were necessary Less effective photoorientation of spin-coated and LbL lms with other polyelectrolyte (PAH, PEI) was attributed to speci c formation of J-aggregates in LbL lms In the LbL lms produced from chitosan and Sunset Yellow (dos Santos et al, 2002), spontaneous birefringence of 0.

04 for the lm of 300-nm thickness was observed; however, the value was not affected by the light This fact underlines the importance of selection of dye and polyelectrolyte Some indications of the in uence of ionic azobenzene derivative structure (Fig 27) and polyelectrolyte can be deduced from a number of azobenzene derivative studied (Ziegler et al, 2002) All studied LbL lms (24 layers) exhibited only out-of-plane orientation Only for anionic-derivative Z1 (indicated in Fig 27) and only with PDADMAC, dichroic ratio of 2 was observed In the layers of Z1, but with PEI as polyelectrolyte, photoorientation and photoisomerization are totally restricted by strong aggregation The high value of dichroism of PDADMAC/Z1 layers should be caused by the hexamethylene spacer of Z1, which results in higher mobility necessary for the orientation process.

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Cationic Z2 Z5 were all manufactured into LbL lms using the same polyelectrolyte PSS, and maximum value of 14 (dichroic ratio) was found Instead of low-molecular-weight azobenzene derivatives, some azobenzenecontaining polyelectrolytes were also employed (Aldea et al, 2007; He et al, 2004; Wang et al, 2004a,b, 1998; Zucolotto et al, 2004b, 2002,; Wu et al, 2001; Lee et al, 2000; ; Balasubramanian et al, 1998; Lvov et al, 1997) By chemical structure, azobenzene-containing polyelectrolytes can be divided into a group with azobenzene moiety situated in the main chain and a group with side-chain azobenzene.

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