AZO POLYMER COLLOIDAL SPHERES: FORMATION, TWODIMENSIONAL ARRAY, AND PHOTORESPONSIVE PROPERTIES in Java

Use QR-Code in Java AZO POLYMER COLLOIDAL SPHERES: FORMATION, TWODIMENSIONAL ARRAY, AND PHOTORESPONSIVE PROPERTIES
AZO POLYMER COLLOIDAL SPHERES: FORMATION, TWODIMENSIONAL ARRAY, AND PHOTORESPONSIVE PROPERTIES
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5.1. INTRODUCTION
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Azobenzene and its derivatives have been extensively used as dyestuffs, pigments, and pH indicators for a long time (Zollinger, 1991). It is well known that azobenzene can exist as trans or cis isomers in the electronic ground state (Rau, 1990). The trans isomer can be converted into cis isomer upon UV light (365 nm) irradiation. The cis-to-trans isomerization readily occurs at room temperature and can be further accelerated by heating or stimulated by visible light irradiation. The trans cis isomerization mechanism and related problems have been intensively investigated by both theoretical calculations and experimental analyses for several decades (see, e.g., Cembran et al., 2004; Schultz et al., 2003; Ishikawa et al., 2001; Cattaneo and Persico, 1999). For the photoisomerization, the transition is related to the motion out of the Franck Condon range on the potential energy surfaces (PESs) of the excited states. Two possible mechanisms of the isomerization have been proposed and tested by different methods. In typical cases, the rotation mechanism attributes the isomerization to the twist around the CNNC dihedral angle, whereas the inversion mechanism ascribes the isomerization to the inversion of one or both of the CNN angles through a linear transition state (Chang et al., 2004; Rau, 1990). Substitution on azobenzene can signi cantly affect the energy gap between the ground and exited states and the isomerization pathways (Crecca and Roitberg, 2006; Schmidt et al., 2004; Biswas et al., 2002; Astrand et al., 2000). The former causes the azobenzene derivatives to possess absorption bands at different wavelengths and exhibit many different hues as dyestuffs and pigments.
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Smart Light Responsive Materials. Edited by Yue Zhao and Tomiki Ikeda Copyright r 2009 John Wiley & Sons, Inc.
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CHAPTER 5: AZO POLYMER COLLOIDAL SPHERES
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The latter can result in a variety of expected and unexpected isomerization behaviors. The problems such as the stable conformation, PESs of the excited states, and isomerization mechanism of the azo compounds are still being explored as active research frontiers. Some puzzling problems as debatable issues still remain in subjects even after persistent study for years. Interested readers can nd more comprehensive reports on these issues in some recent publications (see, e.g., Diau, 2004; Satzger et al., 2004). For real applications, isomerization that can cause color change for dyestuffs had more or less been considered as an unfavorable factor in history for a long time (Zollinger, 1961). Signi cant effort was devoted to prevent the isomerization through some improved molecular designs. This situation has been dramatically changed after early efforts to covalently introduce azobenzene-type chromophores into polymeric chains (Kumar and Neckers, 1989). The azobenzene-containing polymers (azo polymers for short) can show a variety of unique photoresponsive properties triggered by the photoisomerization (Natansohn and Rochon, 2002; Delaire and Nakatani, 2000; Xie et al., 1993). The polymeric materials are expected for the applications in areas such as data storage, optical switching, sensors, and actuators (Yager and Barrett, 2001; Kawata and Kawata, 2000; Xie et al., 1993). Many types of the azo polymers have been designed and synthesized, which include side-chain, main-chain, dendritic azo polymers, and block copolymers (Lambeth and Moore, 2007; Natansohn and Rochon, 2002; Tian et al., 2002; Junge and McGrath, 1999; Archut et al., 1998; Kumar and Neckers, 1989). The azo polymers have been prepared by radical polymerization, step-growth polycondensation, atomic transfer radical polymerization (ATRP), and ring-opening metathesis polymerization (ROMP) among others. 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. 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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