The photolysis of tetra(trifluoromethyl)thiophene (TTFT) at 2139 Å or by mercury sensitization at 2537 Å yields hexafluorobutyne-2 and 1,2,3,4-tetra(trifluoromethyl)5-thiabicyclo[2,1,0]pentene-2 (also called tetra(trifluoromethyl)cyclobutadiene episulfide) as the principal gas phase products. The latter is colored a pale yellow and is stable at room temperature. These results suggest that a possible mechanism for the reaction of photoexcited thiophenes is via the formation of valence bond isomers as intermediates.
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Wiebe et al. (1972) studied this question.