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(Zucolotto et al., 2004b), the structure and charge density of cationic polyelectrolyte PAH can be governed by pH during LbL deposition, and it changes the LbL lms properties. By increasing the pH from acidic to basic, it was possible to increase the bilayer thickness by the factor of 2.4 because of the loose conformation of PAH in the LbL structure. The authors compared the lms with similar amount of azobenzene (the same optical absorption) prepared at different pH and came to the conclusion that an increase in the pH led to a slowing of kinetics of the induction of photoorientation by the factor of 4. For another similar polyelectrolyte PAZO (Fig. 2.8), the data on photoinduced orientation in LbL structures are not available. In contrast to LbL structures, the results on ionic complex of PAZO with PEI (Stumpe et al., 2006a) showed that dichroism was lower in this case compared with the neat PAZO lms (Stumpe et al., 2006b; Goldenberg et al., 2005), approximately proportional to a decrease in azobenzene loading. It seems that there is no restriction of azobenzene motion by ionic interactions with oppositely charged polyelectrolyte in this complex. This demonstrates that the layered structure of the LbL lms should be responsible for this restriction. Two other azobenzene-containing polyelectrolytes (Fig. 2.8) are copolymers. The important difference is that ionizable group (COOH) is attached not to the azobenzene but to another unit on the polymer chain. Therefore, one could expect

A change in the inner potential of the electrode phase by A(p (attained by changing the potential difference of an external voltage source by AE =.

Virtual Iron 3.0/3.1

Some values of association constants are listed in Table 1.1. The dependence of ion-pairing on the dielectric constant is illustrated in the following example. The formation of K + CP ion pairs in aqueous KC1 solutions has not been demonstrated. In methanol (D = 32.6), for KC1,

that ionic interactions, necessary for the LbL organization, will have lower impact on the properties of azobenzene moiety However, some of these copolymers (PBANT-AC, PBACT-AC, PAA-AZ) exhibited only low dichotic ratio (up to 13) (Wang et al, 2004a,b) Other LbL structures with PAA-AN, MA-co-DR13 showed birefringence value up to 0068 (Zucolotto et al, 2002; Lee et al, 2000) It should be noted that spin-coated lms (Lee et al, 2000) showed the same results, and it means that there is no advantage in tedious LbL assembly in this case Also, the authors (Zucolotto et al, 2002) mentioned much longer time necessary to induce maximum value of orientation in LbL systems, and this was attributed to the in uence of ionic and H-bonding interactions In addition, the drier was the LbL lm, the more sluggish was the kinetics of induction of photoorientation.

24 Table 1.1 Values of log K.ass for some ion pairs in aqueous solutions at 25 C (according to C. W. Davies), where indicates that ion pair formation could not be proved IT OH F" -0.08 0.6 3.1 3.9 Na+ -0.7 -0.6 0.7 0.6 1.16 2.4 2.7 K+ -0.2 1.0 0.9 2.3 2.7 Ag+ 2.3 0.4 3.2 4.4 -0.2 1.3 8.8 TT 0.8 0.1 0.5 1.0 0.3 1.4 1.9 Ca 2+ Cu 2+ 1.30 1.0 0.28 2.28 1.95 3.46 6.8 8.1 1.23 0.4 0.0 2.36 Fe 3+ 12.0 6.04 1.5 0.60 1.0

In addition to all the above-mentioned side-chain polyelectrolytes, some azobenzenecontaining polyelectrolytes with chromophore in main chain have been investigated (Fig 28) (Jung et al, 2003; Hong et al, 1999) Unfortunately, only small value of dichroic ratio of about 14 was achieved in this case In contrast to LbL structures, ionic supramolecular complexes (schematically depicted in Fig 22d) can be rst formed in solution and then build into lms The complex formation can be proved by FT-IR and NMR spectra (Zhang et al, 2008; Kulikovska et al, 2007; Xiao et al, 2007; Lin et al, 2003, 2002) In this case, the azobenzene units, although bound with ionic interactions to polymer chains, are devoid of con nement of layered structure The rst observation of photoorientation was recently demonstrated in such polyelectrolyte azobenzene complex of azodye and PEI (Kulikovska et al.

15

P2O74 P 3 O 10 5 "

, 2007; Stumpe et al, 2006a) In the investigated materials, only temporally stable photoinduced anisotropy was found contrary to the glassy polymers Figure 29 displays the induction and relaxation of optical anisotropy in a lm of the material on the basis of PEI and the dye Alizarin Yellow GG (see Fig 27) Irradiation of the lm with 488-nm light gives rise to the orthogonal polarization component of the transmitted probe beam (633 nm) absent in the incident beam, indicating the induction of optical anisotropy After the switch-off of the actinic light, the induced anisotropy relaxes, whereas the relaxation is well described by a two-exponential decay function Alternation of the polarization of the actinic light allows switching off of the induced molecular orientation, as demonstrated in the Fig 29b.