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[摘要]：Nanosecond laser flash photolysis (LFP) expts. show that the rates of ET quenching of triplet benzophenone by 2-alkyldithianes significantly decrease with bulkier substitution. Introduction of sulfur at the b-position of the flexible alkyl chain reverses this trend, whereas such substitution at the a-position has negligible effect. This is rationalized in terms of the three electron two center bonds, favorable due to the formation of five-membered cyclic radical cations in the case of b-substitution, which is supported by DFT computations. |
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