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Azobenzene isomerization volume

Gegiou et found only a very slight viscosity effect, both in the n-Ti and in the jt-jc absorption bands on the isomerization quantum yield. They used glycerol as a viscous solvent, but the result may also be transferred to polymer matrices. In solid matrices, several photoisomerization modes are observed (see the preceding section on the influence of temperature), A com parison between azobenzene isomerization in liquid methylmethacrylate and the slow mode in poly (methylmethacrylate) showed that the difference in quantum yields on Si (0.17) and S2 excitation (0.03) is retained in the solid matrix. The fast process is not observed in n —> n excitation. These data are important in relation to the use of the azobenzene isomerization method for the determination of the free volume in a polymer. [Pg.24]

Isomerization needs some extra sweep volume. The volumes for the two mechanisms of azobenzene should be quite different—ca. 0.25 nm for rotation and ca. 0.12 nm for in version. This bears out in restricted spaces. In some zeolites azobenzene can isomerize whereas stilbene does not. Kuriyama and Oishi found that there are two separate AH versus AS lines for azobenzenes isomerizing by inversion (azobenzene type) and rotation (pseudo-stilbene type). ... [Pg.33]

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... [Pg.116]

The thermal Z —> E isomerization of azobenzene has been widely used to determine free volume in polymers at room and temperatures as low as 4 K.90b9i Jhe thermal reaction is also important in the context of photo-response, as an information written or a signal or state produced by switching E to Z is slowly fading. However, the Z-lifetime is strongly modified by strain in the molecule Z-azobenzene in solution at room temperature has a half life of about 2 days the Z,E E,E isomerization in the [3.3] 4,4 )azo-benzenophane 9 has a half life of ca. 4 min. the [2.2] 4,4 )azobenzenophane 7 has a half life of ca. 15 seconds and in dibenzo[2.2][4.4 )-azobenzeno-phane 8 the life of the E,Z-isomer drops to 1 s. On the other hand, the Z,Z Z,E isomerization in these phanes is slowed down enormously Z,Z-7 lives 2.5 days, Z,Z-9 about 5 days, and Z,Z-10 about 1 year at room temperature. Activation energies are available in the publications. The Z,E E,E isomerization in most azobenzenophanes is very fast. However, in 2,19-Dioxo[3.3](3,3 )azobenzolophane 12, the Z,E-form is relatively stable, The remarkable differences in these and other structures are not due to different activation enthalpies but to different activation entropies. [Pg.20]

Pressure dependence was thoroughly investigated by Asano and his group. It turns out that the partial volumes of the Z-forms of 4-dimethylamino-4 nitorazobenzene and related molecules are ca. 250 cm moP in all solvents. Those of the E-forms are smaller and solvent-dependent. Thermal isomerization rates are weakly dependent on pressure in nonpolar solvents, but contrary to azobenzene- and aminoazobenzene-type compounds, they are strongly dependent in polar solvents in hexane 10%, in acetone 475% for 2100 bar (AV = -0.7 and -25.3 em mol, respectively). This has implications for the discussion of the mechanism of isomerization (Section 1.6). [Pg.30]

The influence of chain packing on the photoisomerization of azobenzene moieties was underpinned by simulations, which also show that sufficient free volume has to be present around the azobenzene moiety for the trans to cis isomerization to occur. [Pg.187]

These examples and investigations on azobenzene moieties in polymers show that the photochromic behavior is mainly Gontrolled by the free volume distribution around the chromophore. Tb obtain LBK films in which azobenzene moieties can undergo photoisomerization, therefore, the free volume around the azobenzene chromophore must be controlled precisely to allow for the molecular rearrangement inherent in the reversible tran to cis photo-isomerization. This is possible by (1) mixing with other amphiphiles, (2) adjusting the architecture of the amphiphile, or (3) attaching the chromophore to a polymer either by coulomb interaction or covalently. [Pg.188]

In polyurethane 33, the azobenzene moieties are separated from each other along the polymer backbone by isophorone units and have the free volume necessary for isomerization and molecular reorientation. This polymer s azobenzene moieties can be photoisomerized readily in mixed LBK films, as demonstrated by measuring the optically induced birefringence that originates from the photoreorientation of the chromophore upon polarized irradiation see Section 6.5.2). [Pg.196]

Another class of polymers equipped with azobenzene moieties comprises a-helical polypeptides, in particular pQly(L-glutamate)s and poIy(L-lysine)s. In solution, these azobenzene-modified polypeptides can undergo photoinduced helix-coil transitions. Polypeptides partially (30 to 50%) substituted with azobenzene moieties are surface active and form stable monolayers. Because of the partial substitution, there is sufficient free volume, and the azobenzene moieties can be isomerized in the monolayer. The photoisomerization changes the area per molecule, and the monolayer shows a photomechanical effect. LBK films of a photosensitive poly(L-lysine) with 31 mol... [Pg.197]

Azobenzene has been incorporated in the shell of hydrophilic microparticles, too. Here, the azobenzene moieties have sufficient free volume for isomerization, as shown by the fact that they can be efficiently reoriented by polarized irradiation (see Section 6.5.2). [Pg.201]

The photoinduced deformation phenomenon of materials is called a photomechanical effect, and it has been so far reported for photoresponsive polymer films and gels [35-43]. When azobenzene is isomerized from the trans form to the cis form, the length of the molecule is shortened from 0.90 to 0.55 nm. The size change of the molecule on photoirradiation is expected to alter the shape of the polymers which contain the azobenzene molecules. However, it is not the case in polymer systems. The transformation in polymer films does not change the polymer shape because of the large free volumes of the polymer bulk. Suitable organization or assembly of the molecules is required for the photoinduced deformation of materials. [Pg.166]

The kinetics of spiropyran and azobenzene photoisomerization deviate from first order when these dyes are entrapped in a solid matrix below Tg.24-34 This behavior has been attributed to the presence of a distribution of free volume within the matrix, as shown in Table 3.11 .35 When the probe is located in sites of free volume Vf greater than the critical volume for isomerization Vfc, the reaction proceeds at the same rate as in solution. For sites of Vf < Vfc, the reaction is retarded, since it becomes controlled by the matrix molecular motions. At low temperature, the local molecular motions are frozen and fluctuations of local free volume become increasingly small as the temperature decreases. Consequently the fraction of sites where Vf < Vk increases. [Pg.136]


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See also in sourсe #XX -- [ Pg.65 ]




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