A low-lying σ* level localized on a sulphur-carbon moiety in p-cyanobenzylthianthrenium trifluoromethanesulphonate allows facile photoinduced molecular rearrangements to occur via an in-cage fragmentation–recombination mechanism involving cation-radical–radical intermediates.
F. D. Saeva, J. Chem. Soc., Chem. Commun., 1987, 37 DOI: 10.1039/C39870000037
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