Temperature photoisomerization

Similar PID results have been reported in very high Tg (up to SSO C) azo-polyimides. It has been shown previously that irradiation of the donor-embedded polyimide derivatives with polarized light alone at room temperature induces a quasi-permanent nonpolar orientation, which can be thermally erased only by heating the polymer above Tg. While, the lifetimes of the polar order generated by thermal poling of the donor-embedded polyimides were found to be on the order of tens of years to centuries at room temperature, photoisomerization can efficiently depole these polymer films in a matter of minutes at room temperature. Indeed, Figure 8.6 shows the effect of p-polarized irradiation on the SH signal of PI-2, which had been previously thermally... 

Figure A3.6.8. Isothemis of k ) for tran.s-stilbene photoisomerization in n-hexane at temperatures between...

Schroeder J, Schwarzer D, Troe J and Voss F 1990 Cluster and barrier effects in the temperature and pressure dependence of the photoisomerization of trans.stilbene J. Chem. Phys. 93 2393-404... 

Dewar thiophenes i.e. 22 and 23) are intermediates in the photoisomerization of cyanothiophenes. Their presence has been demonstrated by trapping and by direct NMR observation (79CC881, 79CC966). The rapid sulfur walk i.e. 22- 23) fully explains the substituent scrambling in the room temperature irradiations (i.e. 21 - 24). 

The first, and to this writing still only case of a ketone a-cleavage-recombi-nation sequence in the steroid field was reported by Butenandt, who found that 17-ketones epimerize at C-13. Ultraviolet irradiation of either stereoisomer produces an equilibrium mixture in which the thermodynamically more favored 13a-compound cf. (15)] with cw-fusion of rings C and D predominates at room temperature. As ultraviolet absorption energies and intensities of the two isomeric ketones are practically identical, the equilibrium composition depends largely on the rate of the competing recombination process from (14). For further examples of the photoisomerization at C-13 of 17-ketosteroids, see ref. 8, 12, 15 and 43. 

The most reasonable mechanism for this transformation, in accord with that suggested by van Tamelen et al. for the dilute acid photolysis, is initial photoisomerization to 2 followed in this case by thermal conversion of the Dewar tropylium ion to 7. The isomerization of 2 to 7 has been reported to be very rapid at temperatures below —60°, and it has been shown, in addition that, in nucleophilic solvents, capture of 2 competes very efficiently with isomerization (Lustgarten et al., 1967). 

It has been found that cyclohexa-2,4- and -2,5-dienones undergo a light-induced valence isomerization reaction in strong acid analogous to the alkylbenzenes, to yield 2-hydroxy-bicyclo[3,l,0]hexenyl cations. The hydroxybenzenium ion (34), for example, underwent a clean photoisomerization to 35 at temperatures below — 60° (Paxrington and Childs, 1970). Cation 35 was also produced upon similar irradiation of 36. 

The validity of the above conclusions rests on the reliability of theoretical predictions on excited state barriers as low as 1-2 kcal mol . Of course, this required as accurate an experimental check as possible with reference to both the solvent viscosity effects, completely disregarded by theory, and the dielectric solvent effects. As for the photoisomerization dynamics, the needed information was derived from measurements of fluorescence lifetimes (x) and quantum yields (dielectric constant, where extensive formation of ion pairs may occur [60], the observed photophysical properties are confidently referable to the unperturbed BMPC cation. Figure 6 shows the temperature dependence of the... 

Irradiation of acetone or methanol solutions of this compound at — 50°C, however, yields the cis photoisomer, which upon warming (0°C), decomposes to yield photoelimination products. This is taken as evidence that the major path at room temperature involves photoisomerization of the trans to cis isomer and rapid thermolysis of the latter. Similar behavior was observed for azobis(isobutyronitrile), azobis(cyanocyclohexane), and azobis(2-methyl-propyl acetate).(4>... 

The results of differential scanning calorimetry(DSC) indicate the change in aggregation state. The trans micelle showed a main endothermic peak at 14 2°C(A H =1.0 kcal/mol), corresponding to a gel-liquid crystal phase transition, whereas the transition temperature for the cis micelle appeared at 11.9°C( AH = 0.8 kcal/mol). This is unequivocal evidence that the trans-cis photoisomerization is a sufficient perturbation to alter the state of molecular aggregation. 

Incidentally, ICD in DPPC liposomes is observed in the temperature range below Tm but not above. Consequently, the non-linear depression of ICD will be relevant to disordering of DPPC molecular arrangement. The change in ICD is a reversible process. Reverse photoisomerization to the trans isomer restores the initial ICD. 

Intriguingly, the conical intersection model also suggests that E,Z-isomerization of acyclic dienes might be accompanied by conformational interconversion about the central bond, reminiscent of the so-called Hula-Twist mechanism for the efficient ,Z-photo-isomerization of the visual pigment rhodopsin in its rigid, natural protein environment101. A study of the photochemistry of deuterium-labelled 2,3-dimethyl-l,3-butadiene (23-d2) in low temperature matrices (vide infra) found no evidence for such a mechanism in aliphatic diene E,Z -photoisomerizations102. On the other hand, Fuss and coworkers have recently reported results consistent with the operation of this mechanism in the E,Z-photoisomerization of previtamin D3 (vide infra)103. 

The E,Z-photoisomerization of previtamin D to tachysterol has also received recent attention. Jacobs and coworkers examined the process in various solvents at 92 K and found evidence for the formation of a triene intermediate which converts thermally (Ea ca 6.5 kcal mol 1) to the more stable tEc rotamer of tachysterol (tEc-T equation 58)230. The rate of this conversion is viscosity dependent. They identified this intermediate as the cEc rotamer, produced by selective excitation of the cZc rotamer of previtamin D. In a re-examination of the low temperature ,Z-photoisomerization of previtamin D as a function of excitation wavelength, Fuss and coworkers have suggested an alternative mechanism, in which tEc-1 is produced directly from cZc-P and cEc-T directly from tZc-P (equation 59)103. This mechanism involves isomerization about both the central double bond and one of its associated single bonds—the hula-twist mechanism of Liu and Browne101 — and involves a smaller volume change than the conventional mechanism for ,Z-isomerization. The vitamin D system has also been the subject of recent theoretical study by Bemardi, Robb and Olivucci and their co workers232. 

When an aqueous solution containing 1,4-dichlorobenzene (190 pM) and a nonionic surfactant micelle (Brij 58, a polyoxyethylene cetyl ether) was illuminated by a photoreactor equipped with 253.7-nm monochromatic UV lamps, photoisomerization took place, yielding 1,2- and 1,3-dichlorobenzene as the principal products. The half-life for this reaction, based on the first-order photodecomposition rate of 1.34 x 10 /sec, is 8.6 min (Chu and Jafvert, 1994). A room temperature rate constant of 3.2 x lO cmVmolecule-sec was reported for the vapor-phase reaction of 1,4-dichlorobenzene with OH radicals (Atkinson, 1985). 

Optically active benzene(poly)carboxamides and benzene(poly)carboxy-lates were used by Inoue and co-workers as sensitizers for the geometrical photoisomerization of (Z)-cyclooctene and (Z,Z)-cyclooctadienes in various solvents at different temperatures. Under energy-transfer conditions, enantiomeric excesses up to 64% ee in unpolar solvents like pentane were reported. The use of polar solvents diminished the product ee s due to the intervention of a free or solvent-separated radical ion pair generated through the electron transfer from the substrate to the excited chiral sensitizer (Scheme 58) [105-109]. 

Considerable data are available concerning the photolysis of m-Cr(en)2(OH)2 +. Thermally, this system was found to give only isomerization to fra 5,-Cr(en)2(OH)2 + photochemically, both isomerization and aquation are observed to occur in proportions which depend upon irradiating wavelength and temperature. Data are given in Table III, from which it is clear that photoisomerization requires an activation... 

Next is the contrast between the 370 m/x to 550 m/x behavior and that for wave lengths greater than 680 m/x. We are now comparing the consequence of exciting a quartet band and a doublet band. The activation energy for photoisomerization has increased to about 13 kcal., and there is a dramatic shift in the aquation behavior which now shows 20 kcal. apparent activation energy and quantum yields approaching unity at low temperatures. The minimal conclusion here is that irradiation of... 

Camphorate complexes of chromium (III) have been studied. The four possible isomers of the tris complex of (+ )-3-acetylcamphorate (173) were isolated,752,753 and absolute configurations were tentatively assigned. The photoisomerization of these complexes has been investigated 754 quantum yields of the order of 10-3 were obtained with visible or ultraviolet radiation at temperatures around 100 °C. Bond-breaking processes were held to be important in the reactivity of cis isomers. 

J. Troe Professor Marcus, you were mentioning the 2D Sumi-Marcus model with two coordinates, an intra- and an intermolecu-lar coordinate, which can provide saddle-point avoidance. I would like to mention that we have proposed multidimensional intramolecular Kramers-Smoluchowski approaches that operate with highly nonparabolic saddles of potential-energy surface [Ch. Gehrke, J. Schroeder, D. Schwarzer, J. Troe, and F. Voss, J. Chem. Phys. 92, 4805 (1990)] these models also produce saddle-point avoidances, but of an intramolecular nature the consequence of this behavior is strongly non-Arrhenius temperature dependences of isomerization rates such as we have observed in the photoisomerization of diphenyl butadiene. 

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