Light-Driven Electron Transfer between a Photosensitizer and a Proton-Reducing Catalyst Co-adsorbed to NiO

While intermolecular hole-hopping along the surface of semiconductors is known, there are no previous examples of electron-hopping between molecules on a surface. Herein, we present the first evidence of electron transfer from the photoreduced sensitizer, Coumarin-343 (C343) to complex 1, both bound on the surface of NiO. In solution, 1 has been shown to be a mononuclear Fe-based proton-reducing catalyst. The reduction of 1 is reversible and occurs within 50 ns after excitation of C343. Interfacial recombination between the reduced 1((-)) and NiO hole occurs on a 100 mu s time scale by non-exponential kinetics. The observed process is the first essential step in the photosensitized generation of Hz from a molecular catalyst in the absence of a sacrificial donor reagent.