Singlet photoisomerization

According to Kramers model, for flat barrier tops associated with predominantly small barriers, the transition from the low- to the high-damping regime is expected to occur in low-density fluids. This expectation is home out by an extensively studied model reaction, the photoisomerization of tran.s-stilbene and similar compounds [70, 71] involving a small energy barrier in the first excited singlet state whose decay after photoexcitation is directly related to the rate coefficient of tran.s-c/.s-photoisomerization and can be conveniently measured by ultrafast laser spectroscopic teclmiques. 

Indazole -> benzimidazole photoisomerization involves a singlet state and has been determined to be monomolecular and monophotonic. The UV spectrum of an intermediate with a lifetime of the order of seconds was recorded. Irradiation of the indazole (526) resulted in a 96% yield of the 1-methylbenzimidazole (528) probably via the intermediate (527)... 

The irradiation of 2- and 3-cyanothiophene gave interesting results in agreement with the scheme described above (Scheme 19). The photoisomerization reaction involved only the excited singlet state and Dewar thiophenes were isolated when the reactions were carried out at -68°C and shown to be intermediates in the isomerization reactions [79JCS(CC)881 79JCS(CC)966]. 

The addition of O2 to acyclic dienes proved to be strongly dependent on terminal substitution and the substituents at other positions of the conjugated system, and, furthermore, it must be accompanied by photoisomerization of ( ,Z)-dienes to ( , )-dienes because singlet oxygen adds exclusively to ( , )-dienes to yield endoperoxides (cf Tables 6(a), 6(b), and 7, and references therein). 

Diphenyl-1,3-butadiene. The excited-state behavior of this diene differs significantly from stilbene and is the subject of a review. Unlike tS in which the lowest vertical excited singlet state is the 1 B state and S2 is the 2 Ag state in solution, these two excited states lie very close to each other in all-trans-1,4-diphenyl-1,3-butadiene (DPB). The additional carbon-carbon double bond introduces a new conformational equilibrium involving the s-trans and s-cis rota-mers. Most spectroscopic studies in solution have concluded that the l B state is S. The DPB compound has a low quantum yield for photoisomerization, so the use of DPB in time-resolved spectroscopic studies on photoisomerization, especially those that monitor only fluorescence decay, needs to be considered cautiously and critically. 

The excited-state behavior of 1,1,2,2-tetraphenylethene (TPE) has been studied by means of picosecond fluorescence, absorption, and Raman spectroscopies and picosecond optical calorimetry. It has been shown that, like stilbene, TPE derivatives substituted with minimally perturbing stereochemical labels such as methyl groups undergo efficient photoisomerization. However, unlike stilbene, strong spectroscopic evidence exists for the direct detection of the twisted excited singlet state, 5ip herein but traditionally designated as of TPE. 

The only recent example of Forster transfer of photochemical importance is the demonstration by Saltiel163 that the ability of azulene to increase the photostationary transjcis ratio in direct photoisomerization of the stilbenes is due entirely to radiationless transfer of excitation from traw.y-stilbene singlets to azulene. As expected for Forster transfer, this azulene effect did not depend upon solvent viscosity. The experimental value of R0, the critical radius of transfer in Forster s formula,181 was 18 A, in good agreement with the value calculated from the overlap of stilbene emission and azulene absorption. 

In the triplet counting technique the substance whose intersystem crossing yield is to be determined is used as a sensitizer for the photoisomerization of piperylene (1,3-pentadiene). Under conditions where essentially all of the sensitizer triplets are intercepted by diene, the quantum yield of isomerization is directly proportional to the intersystem crossing yield of the sensitizer. If the diene interferes with sensitizer singlets however, the yield of triplets will fall, resulting in an anomalously low value for 0,. 

E. Photoisomerization of benzene. Photolysis of liquid benzene by excitation to its (7t, jr ) states brings about interesting photochemical transform ations from vibronically excited singlet as well as triplet states (Figure 7.8). 

The loss of stereochemical memory in the non-vertical excited state implies that stereospecific, concerted reactions of an alkene singlet state may take place from the vertical state. Of particular importance is that the change from cis or trans geometry to something in between opens up a route for converting one geometrical isomer of an alkene to another, and this is a photoisomerization reaction that will be described in the next section. 

The stilbenes absorb light strongly, and their excited singlets cross over to triplets fairly efficiently, from which state photoisomerization occurs. The lowest energy T - S0 absorption bands measured for cis-and rnm-stilbene are at 57 and 48-50 kcal, respectively. However, it is quite likely again that both spectroscopically formed triplets relax very rapidly to a common twisted triplet which decays to both geometric isomers. 

The products obtained upon direct excitation of butadiene,291 norbornadiene,292 cyclohexadiene,293 and other dienes294 are also completely different from those obtained by photosensitization, again demonstrating quite different chemical reactivity of excited singlet and triplet dienes. However, 1,l -bicyclohexenyl295 and 1,3-cycloocta-diene298 represent exceptions, undergoing both direct and sensitized photoisomerizations to cyclobutene derivatives. 

Azobenzene readily undergoes both sensitized and direct cis-trans photoisomerization. However, the sensitized photostationary cis/trans ratios with high-energy sensitizers do not predict those obtained upon direct irradiation, indicating that much of the direct photoisomerization occurs from states other than the lowest triplet.455 As with stilbene, cyclization of the cis isomer apparently is a singlet-state reaction.456... 

Photoisomerization of this type in acetonitrile is not quenched by dienes and the process, therefore, proceeds through the singlet but the yield is dependent on the type of substitution. For example, the 3,5-di-p-tolyl homologue of (365) gives a better yield (77%)... 

These reactions can be interpreted as proceeding via an intermediate of the diazabenzvalene type, formed from the lowest singlet w, it excited state of the pyrazine, and are analogous to the results reported for the photoisomerization of alkylbenzenes.133 Support for this postulate comes from a study of 2,5-dimethylpyrazine which is isomerized to a mixture of 2,5-dimethylpyrimidine and 4,6-dimethyl-pyrimidine, presumably via the two diazabenzvalenes [Eq. (36)]. There is no evidence for products arising via bicyclohexadiene and prismane intermediates which are also involved in the photorearrangement of alkylbenzenes. 

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