Photophysics and photochemistry of sterically strained α-haloanthraquinones: The bromo and/or chloro substituted compounds

The steric hindrance between the oxygen and halogen atoms results in the structural deformation of α-haloanthraquinones and their lowest excited triplet (T₁) states are of mixed nπ ^*-ππ ^* or ππ ^* character with unusually short lifetimes. Moreover, the rates of hydrogen-atom abstraction from ethanol by the T₁ states decrease with their increasing ππ ^* character, and the proximity of the halogen atom to the hydroxy group causes the photochemical intramolecular elimination of hydrogen halide from the initial photoproducts (α-haloanthrahydroquinones) yielding α-haloanthraquinones (or anthraquinone) with one less halogen atom than the original molecule; the final product is anthrahydroquinone. The remarkably large structural deformation of 1,8-dihaloanthrasemiquinone radicals which gives rise to the simultaneous formation of 1,8-dihaloanthrahydroquinones and the original anthraquinones. Of particular interest is observation of the absorption band(s) attributable to the second excited triplet (T₂) states of 1,8-dihaloanthraquinones. However, the electron transfer from triethylamine (TEA) to these T₂ states generating the radical anions is observed only in acetonitrile, while that to the T₁ states generating their exciplexes with TEA is observed not only in acetonitrile but also in toluene and ethanol.