Abstract
AbstractPhotoinduced electron transfer (PET) followed by back electron transfer (BET) reactions of 1,2‐bis(α‐styryl)benzenes 1, generates o‐quinodimethane derivative 2 via the corresponding radical cation 2⋅+. This process serves as a facile method to form o‐quinodimethane intermediates. The intermediacy of 2⋅+ and 2 were confirmed by using various spectroscopic methods and trapping reactions with 3O2 and dienophiles. Kinetic analysis using nanosecond time‐resolved absorption showed that 2⋅+ was transformed to 2 via a BET process, in which the decay of 2⋅+ and rise of 2 have almost the same rate constants of kDECAY=5.6×105 s−1 and kRISE=5.9×105 s−1, respectively. The net BET rate constant evaluated by using Marcus theory is much faster than these experimental values, owing to the reduction based on diffusion.
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