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of thermal and mechanical stabilities, easy processing, and easy integration into devices. Preparation of the photoresponsive hybrid silica materials requires synthesis of azobenzene-containing organosilanes because they are not commercially available. The azobenzene-containing organosilanes were represented by the formula R-Si(ORu)3 in which R contains an azobenzene ligand and Ru is an ethyl or methyl group. After sol gel hydrolysis and condensation of the azobenzenecontaining organodilanes with other silica precursors, the azobenzene-containing R groups are covalently bonded to the silica matrix. Other than the conventional sol gel chemistries toward polysiloxane gels, cohydrolysis and cocondensation of organosilanes and alkyl silicate in the presence of acid or base catalysts and amphiphilic surfactant or block copolymer templates lead to self-assembled highly ordered hexagonal, cubic, or lamellar nanostructures. The nanostructures are controlled by several factors, such as the concentration of silicon precursors and catalyst, amounts of the template molecules, temperature, and aging time. After selective removal of the template molecules, the organofunctional hybrid nanoporous silica materials are created. This surfactant-directed self-assembly technique is utilized to synthesize photoresponsive nanoporous silica materials with azobenzene ligands positioned on the pore surfaces. Under UV and visible light irradiation, the azobenzene ligands undergo trans2cis isomerization and create novel properties of the hybrid silica materials, such as photoregulated mass transport and photocontrolled liquid adsorption. This chapter focuses on azobenzene-containing organosilanes that are precursors for preparing photoresponsive silica materials, mesoporous silica materials with azobenzene moieties on the pore surfaces, and azobenzene-modi ed polysilsesquioxane gels.

/3l [(j3l) + 4j3(2/W -j3 + 1 [03 - I) 2 + 4)3(2 - j3)*:]1/2

This dependence is shown in Fig. 3.10. The usual dependence for n = 2 is obtained for complete disproportionation, that is K 1. With decreasing K, the E~P curve changes and at K = \ assumes the usual shape for n = 1. For small K values three inflection points appear on the curve. This situation often occurs for organic quinones. Form B is then termed the semiquinone. A typical inorganic redox system of this type involves the equilibrium between metallic copper and copper(II) ions. In the absence of a complexformer the disproportionation constant is large and a solution of Cu+ ions is very unstable. However, in the presence of ammonia, copper(I) ions are bonded in a complex, constant K decreases and the E-(3 curve exhibits three inflection points.

Azobenzene-containing organic polymers have been widely investigated in the past several decades for their photoresponsive properties. However, research in azobenzene-containing inorganic polymers, such as sol gel materials, is very limited. As proposed by Ozin and colleagues, a wide range of organic and organometallic precurors are potentially suited for incorporation of organic groups with novel chemical and structural properties into sol gel materials (Maclachlan et al., 2000). Among these precursors, azobenzene-containing organosilane is of particular interest for the preparation of photoresponsive nanocomposite materials. Several efforts have been made to synthetically prepare pendant and bridged azobenzene-containing organosilanes, which are essential for the creation of photoresponsive nanocomposite sol gel materials. Ichimura and coworkers synthesized two organosilanes, 4-methoxy-4u(N-(3-triethoxysilylpropyl)carbamoylmethoxy)azobenzene (MTAB) and 4,4u-bis(N-(3-triethoxysilylpropyl)carbamoylmethoxy)azobenzene (DTAB), using the condensation reaction between carboxylic acid and amine in the presence of dicyclohexylcarbodiimide (DCC; Ueda et al., 1993). However, this synthetic route

Finally, thanks to Elliot Markowitz at Ziff-Davis and Russ Vines for connecting the folks at Wiley with me and suggesting I do this book Barb Foremost, I thank my co-author, Barb Goldworm, for convincing me to help her write this book I ve never had so much fun writing before Her good humor, her passion to get it right, and her ability to laugh under stress got us over some of the tough hurdles I also thank Joan Wrabetz for giving me the final push I needed to go through with this project and for being a constant source of information and inspiration to me Anne Thanks also from both of us to Andrew Kutz for his help in technical editing from a server-virtualization-implementation point of view and to Craig Newell for his help in technical editing from a blade-systems-implementation point of view.

-8 0.8 1.2 Overall oxidation degree,/3 1.6 2.0

is not preferable because of the high toxicity of the DCC compound and the low yields of MTAB and DTAB. Corriu and colleagues also synthesized an azobenzene-bridged organosilane, 4,4u-bis(3-triisopropoxysilylpropoxy)azobenzene (BSPA), and prepared the corresponding photoresponsive hybrid materials (Besson et al., 2005). BSPA was synthesized by reacting 4,4u-dihydroxyazobenzene with 3-iodopropyltriisoproxysilane in the presence of NaH at an elevated temperature of 601C with 70% yield after puri cation. However, two extra steps need to be adopted for the synthesis of 3-iodopropyltriisoproxysilane, which increases the complexity of the synthetic process. Brinker and coworkers designed and synthesized two organosilane precursors, 4-(3-triethoxysilylpropylureido)azobenzene (TSUA) and 4,4u-bis(3-triethoxysilylpropylureido)azobenzene (BSUA), for the preparation of photoresponsive nanocomposite materials (Liu et al., 2003b, 2002). The synthetic routes for TSUA and BSUA are more successful than those for other organosilanes in terms of purity, yield, and simplicity. TSUA and BSUA are new compounds. Some of their novel properties have also been studied.

Fig. 3.10 Dependence of the potential function v = (2F/2.3RT) [E K A,B + B,C)] on the overall oxidation degree J3 for a system with disproportionation. The semiquinone formation constant K' = l/K is indicated at each curve

Both of them added strong insights and helpful additions, not to mention incredibly quick turnaround times, despite their day jobs..