Early events in the photochemistry of 1,2,3-thiadiazole studied by ultrafast time-resolved UV - Vis and IR spectroscopies

Photochemistry of 4-methyl-5-carboethoxy-1,2,3-thiadiazole (MCT) in solution was studied at room temperature using UV - vis and IR transient absorption spectroscopies (λ _ex = 266 nm). Three deactivation pathways are discussed: thiirene formation, thioketene generation, and the internal conversion by repopulating MCT in the ground state. Ultrafast techniques show a very fast rise (<0.4ps) of thiirene species in acetonitrile, possibly as a result of a rearrangement in the singlet excited state of MCT in concert with molecular nitrogen extrusion. The remarkable stability of thiirene in solution on a millisecond time scale is limited by the process of dimerization (thiirene - thiirene, thiirene - thioketene). NMR analysis permitted identification of stable photoproducts as 1,3-dithietane, 1,3-dithiole, and thiophene derivatives. (Figure presented)