Boosting Photoredox Catalysis Using a Two-Dimensional Electride as a Persistent Electron Donor.

Electrides, which have excess anionic electrons, are solid-state sources of solvated electrons that can be used as powerful reducing agents for organic syntheses. However, the abrupt decomposition of electrides in organic solvents makes controlling the transfer inefficient, thereby limiting the utilization of their superior electron-donating ability. Here, we demonstrate the efficient reductive transformation strategy which combines the stable two-dimensional [GdC]·2e electride electron donor and cyclometalated Pt(II) complex photocatalysts. Strongly localized anionic electrons at the interlayer space in the [GdC]·2e electride are released via moderate alcoholysis in 2,2,2-trifluoroethanol, enabling persistent electron donation. The Pt(II) complexes are adsorbed onto the surface of the [GdC]·2e electride and rapidly capture the released electrons at a rate of 10 s upon photoexcitation. The one-electron-reduced Pt complex is electrochemically stable enough to deliver the electron to substrates in the bulk, which completes the photoredox cycle. The key benefit of this system is the suppression of undesirable charge recombination because back electron transfer is prohibited due to the irreversible disruption of the electride after the electron transfer. These desirable properties collectively serve as the photoredox catalysis principle for the reductive generation of the benzyl radical from benzyl halide, which is the key intermediate for dehalogenated or homocoupled products.