Abstract
Abstract Mechanisms of hydrogen atom abstraction reactions by triplet state p-chloranil (3CA) from durene (DH) were studied by picosecond and nanosecond laser photolysis and transient photoconductivity measurements. 3CA was quenched by DH through diffusional encounter to form a triplet ion pair (IP) between CA and DH, p-chloranil semiquinone radical (CAH·), and 2,4,5-trimethylbenzyl radical (D·). Ionic dissociation of IP was observed in 1,2-dichloroethane (DCE) as well as in acetonitrile. However, no transient species was observed by direct excitation of a charge-transfer (CT) band of the electron donor-acceptor (EDA) complex between CA and DH. The H-atom transfer leading to production of CAH· was found to proceed through two distinct mechanisms; H-atom transfer via IP (Mechanism I) and a more rapid transfer competing with IP formation (Mechanism II). The quantum yields of CAH· produced by Mechanisms I and II and the first-order rate constants for proton transfer, ionic dissociation, and intersystem crossing competing with one another in the IP state were estimated to be (0.1 and 0.2) and (2, 5, and 13)×106 s−1, respectively, in DCE at room temperature.
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