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The polymeric backbones not only perform as a good medium with transparent and easy-processable properties but also play an important role in transferring or coordinating the photoisomerization effect of azo chromophores For azo polymers, light irradiation can cause photoresponsive variations such as phase transition (Ikeda et al, 1990), photoinduced chromophore orientation (Todorov et al, 1984), light-driven thin- lm contraction and bending (Li et al, 2003; Yu et al, 2003; Finkelmann et al, 2001), and surface relief grating (SRG) formation (Kim et al, 1995; Rochon et al, 1995) The last but not the least of importance, polymeric chains are able to undergo different self-assembling processes The structures and photoresponsive properties of the azobenzene-containing materials can be dramatically enriched through the self-assembling approaches.

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Self-assembly generally refers to a process in which components, either separate or linked, spontaneously form order aggregates (Whitesides and Boncheva, 2002; Whitesides and Grzybowski, 2002) Self-assembly has been extensively explored to develop a variety of well-de ned structures through bottom-up approaches (Forster and Plantenberg, 2002; Philp and Stoddart, 1996) Azo polymers with specially designed functional groups or chain structures can undergo different types of selfassembly Multilayer thin lms composed of azo polyelectrolytes have been obtained through sequential electrostatic layer-by-layer self-assembly (Laschewsky et al, 1997; Lvov et al, 1997; Wang et al, 1997a) The azo chromophores in the.

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(10,11,. . ,). Intercalation of some guest species, such as alkali metals, can simply be performed via a chemical reaction of a gaseous reactant with graphite. Some other guest species (e.g. H2SO4, HC1O4 and other inorganic acids), however, do not react spontaneously with graphite, but the intercalation can be induced by an auxiliary oxidizing or reducing agent. The redox reaction promo ting intercalation can also be performed electrochemically; the advantage of electrochemical intercalation is not only the absence of any foreign chemical agent and the corresponding reaction by-products, but also a precise control of potential, charge and kinetics of the process. The electrochemical intercalation into graphite leads in the most simple case to binary compounds (graphite salts) according to the schematic equations: Cn + M + + e"-> M + C~ Cn + A - - e ^ C A (5.5.30) (5.5.31)

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In the first case, the graphite lattice is negatively charged and the electrolyte cations, M + (alkali metals, N R | , etc.) compensate this charge by being inserted between the graphene layers. In the second case, anions, A" (CIOJ, AsF^, BF4", etc.) are analogously inserted to compensate the positive charge of the graphite host. Reactions (5.5.30) and (5.5.31) proceed prevailingly during intercalation from solid or polymer electrolytes (cf. Section 2.6) or melts. When using common liquid electrolyte solutions, a co-insertion of solvent molecules (and/or intercalation of solvated ions) very often occurs. The usual products of electrochemical intercalation are therefore ternary compounds of a general composition: M+(Solv)>;Cor C(Solv) y A~

lms can automatically possess the noncentral symmetric alignment, and the thin lms can show the signi cant second-order nonlinear optical (NLO) effect without electric eld poling The electrostatic layer-by-layer lms containing azo chromophores can also show photoresponsive behavior related with the photoisomerization (Wu et al, 2001; Dante et al, 1999) The block copolymer containing mesogenic azobenzene units in one of the blocks has been developed (Morikawa et al, 2006) The polymer can form thin lms with well-organized cylinder structures and photoinduced alignment properties Amphiphilic azo block copolymers have been prepared by ATRP, and light-responsive micellar aggregates have been obtained (Wang et al, 2004) Other recent progresses in the self-assembly of azo polymers can be seen in other chapters of this book This chapter reviews some recent research progresses concerning the colloidal spheres constructed from the polydispersed amphiphilic azo polymers.

The electrochemical intercalation of HSO4 anions together with H2SO4 was described by Thiele in 1934. The composition of the product of prolonged anodic oxidation of graphite in concentrated sulphuric acid is

In contrast to the amphiphilic block copolymers being reviewed in s 6 and 7, the polymers discussed in this chapter are polydispersed amphiphilic azo homopolymers and random copolymers The polymers can be prepared through some relatively simple methods and are easily available from many resources The polymers can form uniform colloid spheres in selective solvent through selfassembling process The colloidal spheres can form ordered two-dimensional (2-D) arrays through vertical deposition, and the 2-D arrays can transform to ordered porous lms through in situ structure inversion In certain sense, these processes can well disclose the essence of self-assembly in which not only components spontaneously form order aggregates but also order can be produced from disorder Such self-assembled structures can be expected to show photoresponsive properties related to both the azo chromophores and the architectures at and beyond molecular level.

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