Triplet-state photophysics and transient photochemistry of cyclic enethiones. A laser flash photolysis study

Abstract

The triplets of four cyclic enethiones, including thiocoumarin, have been investigated by nanosecond laser flash photolysis. Data are presented for transient spectra and kinetics associated with triplets, quantum yields of intersystem crossing and singlet oxygen photosensitization. The quenching of the thiocoumarin triplet (λ^T_max= 485 nm, ε^T_max= 8.8 × 10³ dm³ mol^–1 cm^–1 in benzene) by several olefins, amines and hydrogen donors occurs with rate constants of 10⁷–5 × 10⁹ dm³ mol^–1 s^–1; the lower limits of quantum yields (ϕ_PC) for the related photoreactions, estimated from ground-state depletion, are generally small (0.0–0.11 in benzene, except for good hydrogen donors, namely, p-methoxythiophenol and tri-n-butylstannane). The radical anion of thiocoumarin (λ_max= 405–435 nm) is formed in two stages upon triplet quenching by triethylamine in acetonitrile; the fast component is the result of direct electron transfer to the triplet and the slower component is assigned to secondary photoreduction of the thione ground state by the α-aminoalkyl radical derived from the triethylamine radical-cation.