Single-molecule photoredox catalysis.

The chemistry of life is founded on light, so is it appropriate to think of light as a chemical substance? Planck's quantization offers a metric analogous to Avogadro's number to relate the number of particles to an effective reaction of single molecules and photons to form a new compound. A rhodamine dye molecule serves as a dehalogenating photocatalyst in a consecutive photoelectron transfer (conPET) process which adds the energy of two photons, with the first photon inducing radical formation and the second photon triggering PET to the substrate molecule. Rather than probing catalytic heterogeneity and dynamics on the single-molecule level, single-photon synthesis is demonstrated: the light quantum constitutes a reactant for the single substrate molecule in a dye-driven reaction. The approach illustrates that molecular diffusion and excited-state internal conversion are not limiting factors in conPET reaction kinetics because of catalyst-substrate preassociation. The effect could be common to photoredox catalysis, removing the conventional requirement of long excited-state lifetimes.