Singlets-Driven Photoredox Catalysts: Transforming Noncatalytic Red Fluorophores to Efficient Catalysts.

Red-light absorbing photoredox catalysts offer potential advantages for large-scale reactions, expanding the range of usable substrates and facilitating bio-orthogonal applications. While many red-light absorbing/emitting fluorophores have been developed recently, functional red-light absorbing photoredox catalysts are scarce. Many photoredox catalysts rely on long-lived triplet excited states (triplets), which can efficiently engage in single electron transfer (SET) reactions with substrates. However, triplets of π-conjugated molecules are often significantly lower in energy than photogenerated singlet excited states (singlets). Combined with the inherent low energy of red light, this could limit the reductive/oxidative powers. Here, we introduce a series of sustainable heavy atom-free photoredox catalysts based on red-light absorbing dibenzo-fused BODIPY. The catalysts consist of two covalently linked units: a dibenzo-fused BODIPY fluorophore and an electron donor, arranged orthogonally. Excitation of the dibenzoBODIPY unit induces charge separation (CS) from the donor to the dibenzoBODIPY unit, forming a radical pair (RP) state. Unlike the regular BODIPY counterparts, these catalysts do not form triplets. Instead, SET occurs from the high-energy singlet-born RP states, preventing energy loss and effectively utilizing the low-energy red light. The proximity of donor molecules allows efficient charge separation despite the CS being uphill in energy. The molecules demonstrate efficient catalysis of Atom Transfer Radical Addition (ATRA) reaction, yielding products with high yields ranging from 70 to 90%, while the molecule without a donor group does not exhibit catalytic activity. The mechanistic studies by transient absorption and electron paramagnetic resonance (EPR) spectroscopy methods support the proposed mechanism. The study presents a new molecular design strategy for converting noncatalytic fluorophores to efficient photoredox catalysts operating in the red spectral region.