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Mechanism of Photodimerization of Acenaphthylene

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journal contribution
posted on 30.05.1997, 00:00 by Naoki Haga, Hiroaki Takayanagi, Katsumi Tokumaru
The mechanism of photodimerization of acenaphthylene (ACN) has been investigated in order to elucidate the roles of the singlet and the triplet excited states of ACN in the formation of the Z- and E-dimers in several solvents. The quantum yields and the ratio of the produced Z- to E-dimer were determined under irradiation of ACN at 435.8 nm in several solvents (1,2-dichloroethane, acetonitrile, cyclohexane, benzene, methanol, and DMF) over a wide concentration range (2.0 × 10-4−2.0 M) in the absence of additives and in the presence of 1,2-dibromoethane, a heavy-atom-containing solvent; Eosin-Y, a triplet sensitizer (irradiated at 546.1 nm); and ferrocene, a triplet quencher. On irradiation of ACN in dilute solution, the initially generated S1 state crosses over to the T1 state, though with low quantum yield, before reaction with the ground state ACN can occur due to the very short lifetime of the S1 state, and the resultant T1 state reacts with ground state ACN to give a mixture of the Z- and E-dimers in a ratio that depends on the solvent employed. In more concentrated solution, the S1 state reacts with ACN before intersystem crossing to the T1 state can occur, affording exclusively the Z-dimer.