Multisite PCET with photocharged carbon nitride in dark

A combination of photochemistry and proton coupled electron transfer (PCET) is a primary strategy employed by biochemical systems and synthetic chemistry to enable uphill reactions under mild conditions. Degenerate nanometer‐sized n‐type semiconductor nanoparticles (SCNPs) with the Fermi level above the bottom of the conduction band are strongly reducing and act more like metals than semiconductors. Application of the degenerate SCNPs is limited to few examples. Herein, we load microporous potassium poly(heptazine imide) (K‐PHI) nanoparticles with electrons (e(‒)) and charge balancing protons (H(+)) in an illumination phase using sacrificial agents. e(‒)/H(+) in the K‐PHI nanoparticles are weakly bound and therefore could be used in a range of PCET reactions in dark, such as generation of aryl radicals from aryl halides, ketyl radicals from ketones, and 6e(‒)/6H(+) reduction of nitrobenzene to aniline. The integration of several features that until now were intrinsic for plants and natural photosynthesis into a transition metal free nanomaterial composed of abundant elements (C, N, and K) offers a powerful tool for synthetic organic chemistry.