Journal of the American Chemical Society p. 4404 - 4411 (1985)
Update date:2022-08-16
Topics:
Gorman, A. A.
Hamblett, I.
Irvine, M.
Raby, P.
Standen, M. C.
Yeates, S.
The triplet state of cycloheptatriene (CHT) has been produced by pulse radiolysis in toluene.Its lifetime of 6 +/- 1 μs is considerably longer than for acyclic trienes, ca. 300 ns, despite a smaller energy gap between the relaxed T1 and S0 surfaces.It is proposed that relaxation is from the boatlike spectroscopic state to an approximately planar species within which spin-orbit coupling factors are minimized.Plots of log ket vs. donor triplet energy for endothermic triplet energy transfer to both CHT and the acyclic neo-alloocimene (NA) show that, whereas the latter is close to being a vertical acceptor of triplet energy, CHT exhibits clear "nonvertical" character.In this respect, NA and CHT mimic trans- and cis-stilbene, respectively.It would appear that, for olefinic systems, established "nonvertical" behavior is currently restricted to nonplanar ? systems, and the possibility is raised that such behavior may, at least in part, reflect higher vibrational level densities in such systems.
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