Metal Nanoclusters as Highly Efficient, Versatile Type‐II Photoinitiators via Generating Radicals from Non‐Conventional Hydrogen Donors

Development of highly efficient photocatalysis or photoinitiation systems that are applicable to various types of illumination source is critical to virtually all the light-driven applications. Here, we report a generalizable strategy to achieve highly sensitive, versatile photoinitiation systems based on the combination of metal nanoclusters with non-conventional hydrogen donors (co-initiators). Discovery of this type-II photoinitiation pathway in metal nanoclusters not only improves their two-photon initiation sensitivity by up to three-orders-of-magnitude, it further opens the door for metal nanoclusters to trigger the photopolymerization using the low-power UV light-emitting diodes. Different from molecular type-II photoinitiators, we found that the selection rules of hydrogen donors for metal nanoclusters are largely dependent on their ligand structures. More importantly, using electron paramagnetic resonance and mass spectroscopy, we for the first time demonstrate that the photoexcited metal nanoclusters can function as versatile hydrogen atom abstractors which generate various types of previously unreported thiyl and nitrogen-centered radicals. This finding indicates the broad opportunity of the future application of metal nanoclusters in light-driven organic synthesis and radical chemistry.