Abstract
In this work, we characterized the direct photochemistry of a set of five structurally-related 1,3,5-trithianes. The compounds were 1,3,5-trithiane, the α- and ÎČ-isomers of the 2,4,6-trimethyl derivatives, and the α- and ÎČ-isomers of the 2,4,6-triphenyl derivatives. Under steady-state, 254-nm irradiation of acetonitrile solutions of all five trithianes, dithioesters of the form RC( = S)SCH(R)SCH 2R were identified and shown to be primary photoproducts (R = H, CH 3, or C 6H 5). Shorter dithioesters, RC( = S)SCH 2R, were also identified and shown to be secondary products. The presence of the dithioesters could be monitored by their strong absorption bands in the region of 310 nm. This same band was evident following the laser flash photolysis of the five trithianes. The laser-induced transient spectra showed another absorbing species ( I) in all five trithianes. This species was not stable and showed a complementary decay that matched the growth of the stable photoproducts at 310 nm. This suggested that the intermediates ( I) are the precursors of the corresponding dithioesters, RC( = S)SCH(R)SCH 2R. These correlated processes were related to monophotonic events. However, in the laser flash photolysis experiments in the triphenyl derivatives, there was an additional pathway for the formation of the dithioesters, and this was biphotonic. When the biphotonic formation of products was compensated for, RC( = S)SCH(R)SCH 2R formation quantum yields from steady-state and laser flash photolysis matched within experimental error. The absorption band of ( I) varied systematically with substituents, 320 nm in 1,3,5-trithiane, 340 nm in the 2,4,6-trimethyl derivatives, and 420 nm in the 2,4,6-triphenyl derivatives. The nature of these intermediates ( I) were discussed as resulting from C S bond cleavage, probably heterolytic.
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More From: Journal of Photochemistry & Photobiology, A: Chemistry
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