Spectroscopy and Reactivity of Kekulé Hydrocarbons with Very Small Singlet−Triplet Gaps

Two Kekulé hydrocarbons, 2,2-dimethyl-2H-benzo[cd]fluoranthene (1) and its benzannellated analogue 2,2-dimethyl-2H-dibenzo[cd,k]fluoranthene (2), were generated photochemically from two different photoprecursors each and investigated spectroscopically in cryogenic matrices by UV-vis, fluorescence, and EPR and in solution using ns flash photolysis and chemical trapping experiments. Hydrocarbon 1 is a ground-state singlet species, whereas compound 2 has a triplet ground state, the first such neutral Kekulé hydrocarbon. This difference, which is supported by density functional calculations, has profound influence on the spectroscopy and reactivity of the two compounds. Using the results of the spectroscopic measurements, trapping experiments, and density functional calculations, the singlet-triplet gap for 1 is estimated to be 2.3-2.8 kcal mol(-1), with the singlet the ground state, and 0.8-1.3 kcal mol(-1) for 2, in favor of the triplet.