An efficient and benign method of C (sp3)‐H acylation based on the direct conversion of stable amides has been established. This photoredox cross‐coupling of amides and methylbenzenes for aromatic ketones is enabled by the cheap benzophenone photocatalyst and nickel catalyst, with high yield (up to 90 %). The benzophenone catalyst having electron‐withdrawing group promotes the efficiency of hydrogen atom transfer, which is beneficial to improve the yield.

Four novel heteroleptic Cu(I) photosensitizers with 3,8‐diaryl‐2,9‐diisopropyl‐1,10‐phenanthroline derivatives as electron‐donating bidentate N‐ligands have been designed and synthesized. The metal copper complexes are studied in light‐driven water reduction system. And the substituent effect at the 3,8‐positions of N‐ligands impacting on photosensitive activity and photoelectric chemical properties are explored and discussed. Surprisingly, with the enhancement of electron‐donating capacity of substituent group at 3,8‐sites of 1,10‐phenanthroline, the photosensitive activity of photosensitizer linearly increases, and photocatalytic performance up to 817 turnover numbers (TON) was reached combining with water reduction catalyst (WRC), Fe3(CO)12. The photocatalytic performance of these photosensitizers dramatically increased compared to 2,9‐diispropyl‐1,10‐phenanthroline complex (TON = 89). Moreover, the introduction of methoxy substituent to copper complexes, which could increase the fluorescence lifetimes (τmax = 209 ns) and promote hydrogen evolution.