Azobenzene derivatives

Many workers have used the cis-to-trans stmctural change referred to above and brought about by UV irradiation to change some physical parameter of the LB films fonned from azobenzene derivatives [55, 56, 57, 58, 59 and 60],... 

Nakahara H and Fukuda K 1983 Orientation of chromophores in monolayers and multilayers of azobenzene derivatives with long alkyl chains J. Colloid Interface Sol. 93 530-9... 

Jones R, Tredgold R H, Hoorfar A, Allen R A and Hodge P 1985 Crystal-formation and growth in Langmuir-Blodgett multilayers of azobenzene derivatives—optical and structural studies Thin Solid Films 134 57-66... 

Tredgold R H, Allen R A and Hodge P 1987 X-ray-diffraction and optical studies of Langmuir-Blodgett films formed from azobenzene derivatives Thin Solid Films 155 343-52... 

Nishiyama Kand Fujihira M 1988 Cis-trans reversible photoisomerization of an amphiphilio azobenzene derivative in its pure LB film prepared as polyion oomplexes with polyallylamine Chem. Lett. 1257-60... 

Nakahara H, Fukuda K, Shimomura M and Kunitake T 1988 Moleoular arrangements and photoisomerization of amphiphilio azobenzene derivatives in monolayers and multilayers Mppo/ Kagaku Ka/sh/1001-10... 

Organic synthesis 38 [OS 38] Formation of an azobenzene derivative from N,N-dimethylaniline with 4-nitrobenzenediazonium tetrafluoroborate... 

The synthesis of N,N-dimethylaniline with 4-nitrobenzenediazonium tetrafluoroborate yielded the corresponding azobenzene derivative [107] (see also [14]). 

Organic synthesis 39 [OS 39) Formation of azobenzene derivatives for pigment production... 

OS 38] [reactor and protocol given in [107]] By reaction of N,N-dimethylaniline with 4-nitrobenzenediazonium tetrafluoroborate, the corresponding azobenzene derivative is obtained at a conversion of 37% using methanol (protic solvent) or acetonitrile (aprotic solvent) under electroosmotic flow conditions [107] (see also [14]). 

The compound exists normally as the trans or ( )-isomer 21a. This molecule is essentially planar both in the solid state and in solution, although in the gas phase there is evidence that it deviates from planarity. When irradiated with UY light, the ( )-isomer undergoes conversion substantially into the cis or (Z)-isomer 21b which may be isolated as a pure compound. In darkness, the (Z)-isomer reverts thermally to the (F)-isomer which is thermodynamically more stable because of reduced steric congestion. Some early disperse dyes, which were relatively simple azobenzene derivatives introduced commercially initially for application to cellulose acetate fibres, were found to be prone to photochromism (formerly referred to as phototropy), a reversible light-induced colour change. C. I. Disperse Red 1 (22) is an example of a dye which has been observed, under certain circumstances, to give rise to this phenomenon. 

ZnS04 MnS04 A12(S04)3 and MgS04 anhydrous salts good for azobenzene derivatives, A12(S04)3 for hydroxyl anthraquinones, and... 

In the case of stearate ions intercalated in Mg/Al LDHs, the electron density shows a pronounced minimiun in the center of the interlayer region, which is consistent with the presence of a bilayer of guest molecules [151,152], The electron density distribution for an anionic azobenzene derivative intercalated in an Mg/Al LDH has also been reported [ 153]. 

Although not strictly to be included in this section it is worth comparing the azobenzene-derived EGB s with those generated from azines. The azine-derived bases are of similar strength to the azobenzene radical-anions, as evidenced by their ability to deprotonate phosphonate esters(Table 15, p. 160). 

The difficulty in judging the nature of the effective EGB has been referred to in the context of azobenzene-derived bases (Scheme 12 and discussion on p. 139). In those cases, in cyclic voltammetric experiments, the reversible first reduction peak becomes irreversible in the presence of weak acids with an approximate doubling of cathodic... 

The incorporation of a cationic azobenzene derivative, p-( a> -dimethyl-ethanolammonioethoxyj-azobenzene bromide, into nanoporous silica films and the photochemical reactions of the adsorbed dye were investigated. The nanoporous silica films were prepared from tetramethoxysilane and octadecyltrimethyl-ammonium chloride by the rapid solvent evaporation method which we have reported previously. The adsorption of the cationic azo dye was conducted by casting an ethanol solution of the dye onto the nanoporous silica films. Upon UV light irradiation, trans-azobenzene isomerized photochemically to the c/s-form and photochemically formed c/ s-form turned back to the frans-form upon visible light irradiation. The nanoporous silica films were proved to be an excellent reaction media to immobilize organic photocromic species. 

We now report the photochromic reaction of an azobenzene in the nanoporous silica film. Since the photochromic behavior is environmentally sensitive, photochromism of organic substances in solid matrices has been investigated to understand as well as to modify the photochromic behavior.[21] Photochromism of azobenzene and its derivatives due to cis-trans isomerization (Scheme I) has widely been investigated. Photocontrol of chemical and physical functions of various supramolecular systems has vigorously been studied by using photochemical configurational change of azobenzene derivatives.[22,23]... 

Studies by Nishiyama and Fujihara [149] utilizing azobenzene derivative (27) as isomerizable chromophores have demonstrated the importance of reaction cavity free volume in L-B films. The L-B films of amphiphilic derivative 4-octyl-4 -(3-carboxytrimethyleneoxy)-azobenzene (27) upon irradiation was found to be stable, no geometric isomerization of the azobennzene moiety occurred. This compound forms L-B films with water soluble polyallylamine 28 at an air-water interface. Reversible cis-trans photoisomerization occurs in the film containing 28. The reversible photoisomerization reaction in polyion complexed films is thought to occur because of the increased area per molecule provided in the film. The cross sections of molecule 27 in the pure film and in film containing 28 were estimated to be 0.28 and 0.39 nm2. Such an increased area per molecule... 

Figure 23. (a) Schematic representation of an anionic surfactant azobenzene derivative monolayer film at the air-water interface. (i>) Schematic representation of the stable monolayer film formed from the polyion complex of anionic surfactant azobenzene derivatives with a cationic polymer. Note the difference in free volume around the reactant chromophores in the two monolayers. 

Figure 4.4. Azobenzene derivatives, (a) Materials discussed in [35> 151] ancj jn the text, (b) Azobenzene materials discussed in [152, 153] and in the text R is a simple hydrocarbon chain which was varied in length in the studies referred to, as was the number of CH, groups which is denoted by n.

If one makes use of the rather limited information available and given above one may infer that a tilt of between 20° and 30° is normal for straight chain azobenzene derivatives when deposited as LB films, even when a homeotropic phase exists. Such a structure can only be produced in a rather loosely packed film. At the moment it is an open question whether monolayers of these materials exist in the hexatic phase as is the case for fatty acids or whether the structure more nearly corresponds to the smectic-A phase. In the case of the birefringent phase described by Jones et al. [151] it was shown that, once this phase was established, further layers deposited by the LB technique go down in an epitaxial manner. 

Many other papers dealing with azobenzene derivatives deposited by the LB technique have been published during the past few years, though, for the most part, they have only an indirect relevance to the main theme of this book. A brief selection of these papers is given here. Tanaka et al. 

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