Interactions Involving Triplet State and Phosphorescence

The role of the triplet state in the cis-trans isomerization of stilbenes effected by photosensitizers, such as acetophenone, benzophenone, or anthraquinone, which have large So Ti excitation energies, was first revealed in Ref. [65]. Theoretical considerations and experimental data on intermolecular triplet-triplet energy transfer leading to the sensitized stilbene photoisomerization are described in Section 4.2.2. It was shown that data on positional dependence of the heavy-atom effect on the cis-trans photoisomerization of bromostilbenes were consistent with the fact that, in contrast to the para position, the meta position is near a node in the highest occupied and the lowest unoccupied MO of stilbene [66]. According to [67], internal and external heavy-atom effects induce phosphorescence in frans-stilbene 

The electronic spectroscopy of trans-isomers of 3-(N-phenylamino)stilbene (mlc), 3-(N-methyl-N-phenylamino)stilbene (mid), 3-(N,N-diphenylamino)stilbene (mle), and 3-(N-(2,6-dimethylphenyl)amino)stilbene (mlf) and their double-bond constrained analogues, m2a-m2c and m2e, were studied [71]. When compared with trans-3-aminostilbene (mla), mlc-mle displayed a redshift of the So — Si absorption and fluorescence spectra, lower oscillator strength and fluorescence rate constants, and more effldent Si — Ti intersystem crossing. The N-Ph derivatives mlc-mle had lower fluorescence quantum yields and higher photoisomerization quantum yields. The role of Si — Ti transition in the amino-substituted stilbenes as the predominant nonradiative decay pathway was discussed. The excited triplet (Ti) state formation of stilbene dendrimers (tetramethoxystilbene (generation G) GO, Gl, 

and G4) was observed [72]. From time-resolved studies on energy and molecular volume changes, it was found that the conformational change completes with the decay of the Ti state for G0-G2. The dynamics was slightly slower for G4, which is attributed to the conformational change of the dendron part. 

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