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At the same time, SRG could be readily inscribed onto the spin-coated layers of the same polymer (Lee et al, 2000) Some light-induced surface modulation was also observed for PBACT-AC and PBANT-AC polyelectrolytes (Fig 28) multilayers lms The SRG amplitude was really small, which corresponds quite well with the spin-coated lm of PBANT-AC that also yielded only 85-nm deep SRG (Wang et al, 2004b) Similar results (16-nm amplitude after ca 40-min writing) were obtained for PA AZ CA (Fig 28) layers (He et al, 2004) For PAA-AZ LbL multilayers, any surface modulations have been observed (Wang et al, 2004a) Also, in this case, one cannot exclude that holographic writing conditions were not optimized For polyelectrolyte PS-119 (Fig 28), a dependence of recording rate on pH upon lm preparation similar to that discussed earlier for photoorientation has been found (Zucolotto et al, 2004b).

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Gratings of 26- and 12-nm depth were obtained after 2-h writing in the lms produced at pH 4 and pH 10, respectively It was associated with higher free volume available in lms produced at low pH When the same azobenzene-containing polyelectrolyte (PS-119) was alternated by charged dendrimers (dos Santos, 2006), higher ef ciency for low generation dendrimer was obtained (SRG amplitude of 30 nm) However, all these values were rather small, which bring the question about what might have been the reason for the low ef ciency of the grating formation in LbL systems In the authors opinion, it is closely related to the mechanisms of grating formation in these systems Is it the light-driven motion of chromophores dragging the inert polymer chains by means of ionic interactions in adjacent layers (Zucolotto et al.

, 2004a), whereas the latter suppresses the reversible isomerization of azobenzene and, at the same time, the con nement to the layers hinders any translation motion Or are there other mechanisms, such as photodegradation (bleaching) (He et al, 2000), that may dominate the formation of grating Nevertheless, the applied approach, demonstrating the inscription of SRG in materials with ionic interactions, presents a new insight into physics of lightinduced mass transport in azobenzene-based materials The importance of this approach is particularly enhanced by the possibility of the unique, molecularlevel control over the material properties (Oliveira et al, 2005; Halabieh et al, 2004)..

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A different supramolecular approach has been successfully used to design azobenzene-containing materials capable of very effective SRG formation (Kulikovska et al, 2007; Stumpe et al, 2006a) The materials consist of ionic complexes of polyelectrolytes and oppositely charged azobenzene derivatives as counter ions Fig 22 explains schematically the material structures in comparison to the conventional azobenzene-containing materials reported for SRG inscription For the rst time, a very effective light-induced mass transport even superior to that in the functionalized polymers has been demonstrated in the systems, where the chromophores are attached to the passive polymer chains by the noncovalent interactions SRGs with the surface modulation depth up to 165 mm have been obtained using these materials.

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Formation of such deep relief structures evidences that alternatively to covalent bonding, the ionic interactions keep the chains of passive polymer linked to the chromophores, strongly enough to be involved into the light-induced motion of chromophores Since the interactions between azobenzene moiety and a polymer matrix became of particular importance in this latter case of the light-induced mass transport, a few studies on noncovalent intermolecular interactions that have been widely exploited in supramolecular chemistry are discussed They were used, for example, to prepare self-assembled materials (Meier and Schubert, 2005; Pollino and Weck, 2005; Faul and Antonetti, 2003; Ikkala and ten Brinke, 2002) A number of polyelectrolyte surfactant complexes that form lms with low surface energies have been reported (Thunemann et al, 2000, 1999; Antonietti et al, 1994).

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