Azobenzenes structure, photoisomerization

Stilbene and azobenzene cause photoisomerization between trans and cis forms, and their structures are simple enough to provide many derivatives thus various combinations with transition metals have been reported. Ru11 complexes with both trans and cis forms of 4-stilbazole (stpy), Ru(bpy)2(fra s-slpy) (43a) and Ru(bpy)2(cz s-stpy) (43b) have been synthesized by Whitten et al., and the trans/cis ratio (Dc/t) of each in the photo-... 

Azobenzene-containing polymers are reported in the literature at a rate of about 150 papers/year for the last five years. There are two main directions of interest the first relates to the donor-acceptor substituted azobenzenes as the structure generating second-order polarizability and - by noncentrosymmetrical alignment - second order nonlinear optical properties in poled films. The second direction of interest is related to the photoinduced isomerization between the trans (more stable) and cis configurations of the azobenzene. This photoisomerization has a wealth of unexpected and useful consequences which were noted only in the last decade. Both these directions appeared because of the availability of lasers, which on the one hand allowed the observation of the nonlinear optical properties and on the other hand... 

Molecular opto-electronic assemblies, which consist of a functionalized gold electrode with a photo-isomerizable redox-activated monolayer, enables amperometric transduction of the photonic information recorded by the interface. On-off operation of superstructure formation of hermaphroditic cyclodextrin derivatives is brought about by disturbing the monomer/dimer equilibrium of -azobenzene structures by photoisomerization. When the structures have the Z-form, the dimer dissociates. The thermal Z— isomerization can be enhanced by heating in favor of the dimer formation (Figure 89.8). ... 

Two commercial disazo disperse dyes of relatively simple structure were selected for a recent study of photolytic mechanisms [180]. Both dyes were found to undergo photoisomerism in dimethyl phthalate solution and in films cast from a mixture of dye and cellulose acetate. Light-induced isomerisation did not occur in polyester film dyed with the two products, however. The prolonged irradiation of Cl Disperse Yellow 23 (3.161 X = Y = H) either in solution or in the polymer matrix yielded azobenzene and various monosubstituted azobenzenes. Under similar conditions the important derivative Orange 29 (3.161 X = N02, Y = OCH3) was degraded to a mixture of p-nitroaniline and partially reduced disubstituted azobenzenes. 

The photoisomerization of several copolymers was studied, in order to determine the effects of the structure and switching of the chiral side chain on the helicity of the main chain. A delicate balance of parameters was found, including separation and nature of the stereocenters, solvent, and concentration of azobenzene moieties J77 Stereoselectivity was often greatly enhanced if the chiral moieties were closer to each other. Accordingly, it was found that the incorporation of the stereocenter into a short, two-carbon spacer resulted in much more pronounced helical preference, as well as CD effects at lower chiral chromophore concentrations. The greater helical twist and improved thermal stability of the cis form (half-life 40h at RT) are notable features. 771 It was also found that the relationship between the trans-cis... 

Photoresponsive polymers can be obtained by introducing photochromic units, such as azobenzene or spiropyran groups, into the macromolecules of polymeric compounds. As described in Chapter 1 of this book, photochromic compounds can exist in two different states, such as two isomeric structures that can be inter-converted by means of a light stimulus, and the relative concentrations of which depend on the wavelength of the incident light. For instance, in azobenzene compounds, photochromism is due to trans-cis photoisomerization around the N=N double bond, while in spiropyran compounds photochromism involves interconversion between the neutral spiro form and the zwitterionic merocyanine form (Figure 1). 

The conformational behavior can be quite different in aqueous solution. Below pH 5, a sample of poly(L-glutamic acid) containing about 30 mol% azobenzene units adopts a P-structure that is not affected by light. Above pH 7, the polypeptide is random coil and the conformation is, once more, not affected by the photoisomerization of the azo side chains. However, at pH values in the range 5-7 (close to the pK of the conformational transition), irradiation causes a remarkable diminishing of the ordered structure, which is completely reversed in the dark.120,221... 

Poly(L-lysine) containing azobenzene units linked to the side chains by means of a sulfonamide function (Scheme 4, Structure VI), was obtained by treating poly(L-lysine) with p-phenylazobenzenesulfonyl chloride. The poly(a-amino acid) was modified quantitatively conversion to the azo-lysine units of VI was effectively 100%. The azo-modified polypeptide was soluble in HFP, in which it exhibited an intense photochromism attributed to the trans-cis photoisomerization of the azobenzene units. Like other sulfonated azobenzene compounds, 33 azosulfonyl-modified polymers of L-lysine were found to be very stable in their tis form, and no thermal decay was observed at room temperature over periods of times as long as several weeks. Interconversion between the two forms at room temperature could only be effected by irradiation at appropriate wavelengths. This behavior allowed the authors to purify the trans and cis forms of the model compound NE-azobenzenesulfonyl-L-lysine (VII) by chromatography, and to measure the absorption spectra of the two pure photoisomers. 

Kinoshita et alJ107,l0x used poly(L-glutamic acid) containing 12-14 mol% azobenzene units in the side chains (Scheme 3, Structure III) to prepare membranes obtained by coating a porous Millipore filter with a 0.2 % chloroform solution of III. Irradiation at 350 nm was found to increase the membrane potential and crossmembrane permeability. The photoinduced alterations of the membrane functions were completely reversible and could be controlled by irradiation and dark-adaptation, in correlation with the trans-cis photoisomerization of the azobenzene units. 

The compound XXIII, consisting of two amphiphilic helical rods linked by an azobenzene moiety, was found to form micelles and ordered aggregates in aqueous solution in the dark, when the azo moiety is in the trans configuration. Photoisomerization of the azo linkage into the cis configuration, and the consequent bending in the structure of the molecules, induced disaggregation and disruption of the micelles.1118,1191... 

Figure 18.5 Control of mass transfer through an azobenzene-modified film, (a) Structure and photoisomerization of azobenzene (b) structures of ferrocene derivatives used to monitor anodic current at the film-electrode interface and (c) current as a function of light exposure for FDM and FDMDG redox probes.57 (Reprinted with permission from N. Liu et al., Nano Lett. 2004, 4, 551-554. Copyright 2004 American Chemical Society.)...

Two kinds of photoresponsive azobenzene polyurethane functionalized multiwalled carbon nanotube (AzoPU-MWNT) composites were synthesized by in-situ polycondensation (50). Core-shell structures with MWNTs as hard core and polymer layer as soft shell were formed and the average thickness of the grafted polymers was about 7-10 nm. The AzoPU-MWNT composites showed reversible photoisomerism behavior. 

As mentioned above, the sol-to-gel phase transitions can be induced reversibly by trans-cis photoisomerization of the azobenzene groups. UV irradiation (330 < X < 380 nm) transforms a part of the trans isomers to the cis. As a consequence of the structural change, the gel state is switched to the sol. Visible irradiation (at X > 460 nm) isomerizes the cis isomers to their trans form and allows the gel to be re-established. The reversible photocontrol of the sol-to-gel phase transition can be monitored by CD spectroscopy. 

There are, however, azobenzenes that have wavelength-independent isomerization quantum yields and thus obey Kasha s rule. The structure of these molecules inhibits rotation. Rau and Liiddecke investigated azobenzeno-phane 9 and Rau the azobenzene capped crown ether 14, and these researchers found identical E,E —> E,Z, and E —> Z quantum yields respectively, regardless of which state was populated. The photoisomerization of azobenzenophanes and 13 could not be evaluated in the same way because the photoisomerization is intensity-dependent. A series of azobenzenes substituted in all ortho positions to the azo group has equal quantum yields for n —> n and k —> k excitation if the substituents are ethyl, isopropyl, tert.butyl, or phenyl. This provides clues for the elucidation of the isomerization mechanism (Section 1.6). 

Yoshii, K., Machida, S., and Horie, K. (2000). Local free volume and structural relaxation studied with photoisomerization of azobenzene and Persistent Spectral Hole Burning in poly(alkylmethacrylate)s at low temperatures. /. Polym. Sci. B Polymer Physics 38, 3098-3105. 

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