The two-electron reduced forms of perylene diimides (PDIs) are luminescent closed-shell species whose photochemical properties seem underexplored. Our proof-of-concept study demonstrates that straightforward (single) excitation of PDI dianions with green photons provides an excited state that is similarly or more reducing than the much shorter-lived excited states of PDI radical monoanions, which are typically accessible after biphotonic excitation with blue photons. Thermodynamically demanding photocatalytic reductive dehalogenations and reductive C-O bond cleavage reactions of lignin model compounds have been performed using sodium dithionite acts as a reductant, either in aqueous solution or in biphasic water-acetonitrile mixtures in the presence of a phase transfer reagent. Our work illustrates the concept of multi-electron reduction of a photocatalyst by a sacrificial reagent prior to irradiation with low-energy photons as a means of generating very reactive excited states.
Keywords: electron transfer; luminescence; photocatalysis; photochemistry; photophysics.
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