Congratulations to the Scott group at Bath, Gabi Hierlmeier and Joshua for our study just published in ACS Catalysis on the photochemical reactivity of authentically glovebox-isolated radical anions!
When chemists probe transition metal catalysis, a logical approach is to isolate intermediates from the catalytic cycle. Yet, surprisingly this is rarely done in photoredox catalysis, a field that is supposed to be 'mature' after almost 2 decades of renaissance!
So, the team led by Daniel set about to prepare and isolate radical anion photocatalysts whose intermediacy has been a topic of some debate. We unequivocally demonstrated that these picosecond-lived species are the photoactive species that engage unactivated aryl chlorides in SET reductions, contrary to the proposals of some that the radical anion photocatalysts decompose to closed-shell species during their reactions (the closed-shell decomposed species, if relevant, are limited to 'activated' EWG-substituted aryl chlorides)
Also curious was their wavelength dependance behaviour, that EWG-substituted aryl chlorides can be engaged with red light, but unactivated ones need higher excited states!
Check out these beautiful crystal structures of isolated DCA and NpMI radical anions!
A privilege to have contributed to this landmark paper on the mechanisms of radical ion photocatalysis. Congratulations especially to Sam and Daniel!
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Looking forward to future collaborations and exchanges
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