Nanorod Photocatalysts for C−O Cross‐Coupling Reactions

Abstract Carbon‐heteroatom cross‐coupling reactions are significant for numerous industrial chemical processes, in particular for the synthesis of pharmaceuticals, agrochemicals, and biologically active compounds. Photocatalyst/transition metal dual catalytic systems pave a new avenue for organic cross‐coupling reactions. Specifically, the use of semiconductor nanoparticles as heterogeneous light sensitizers is highly beneficial for industrial‐scale applications owing to their low‐cost production, tunable photophysical properties, facile separation, high photostability, and recyclability. Here, CdSe@CdS nanorod photocatalysts are combined with a Ni complex catalyst for the promotion of selective light‐induced C−O cross‐coupling reactions between aryl halides and alkyl carboxylic acids. This efficient dual photocatalytic system displays a high yield (∼96 %), with an impressive turnover number (TON) of over 3×10 6 , and within a relatively short reaction time as a result of high turnover frequency (TOF) of ∼56 s −1 . In addition, the nanorod photocatalysts harness light with improved solar to product efficiency compared to alternative systems, signaling towards potential solar‐powered chemistry. A reaction mechanism involving energy transfer from the nanorods to the Ni complex is proposed and discussed, along with specific benefits of the seeded rod morphology.