Reactivity control of a photocatalytic system by changing the light intensity.

We report a novel light-intensity dependent reactivity approach allowing us to selectively switch between triplet energy transfer and electron transfer reactions, or to regulate the redox potential available for challenging reductions. Simply by adjusting the light power density with an inexpensive lens while keeping all other parameters constant, we achieved control over one- and two-photon mechanisms, and successfully exploited our approach for lab-scale photoreactions using three substrate classes with excellent selectivities and good product yields. Specifically, our proof-of-concept study demonstrates that the irradiation intensity can be used to control (i) the available photoredox reactivity for reductive dehalogenations to selectively target either bromo- or chloro-substituted arenes, (ii) the photochemical cis-trans isomerization of olefins versus their photoreduction, and (iii) the competition between hydrogen atom abstraction and radical dimerization processes.