Photochemical C-H activation and subsequent aerobic oxidation reactions of benzene with Cp*Ir(CO)2

► Photochemical C-H activation and aerobic oxidation of benzene with Cp*Ir(CO)2 were reported. ► Some interesting iridium complexes were formed. ► A novel hexanuclear iridium cluster with Ir25+ cores was reported. ► The reactivities of some obtained iridium complexes were studied. ► These results may help us gain more insights into the reactivity of iridium-hydrogen complexes toward oxygen and promote their application in catalysis.