Efficient activation of dioxygen (O₂) under mild and environmentally friendly conditions remains a challenging yet crucial area of research in chemistry.In this study,we present a simple yet effective approach for O₂ ...Efficient activation of dioxygen (O₂) under mild and environmentally friendly conditions remains a challenging yet crucial area of research in chemistry.In this study,we present a simple yet effective approach for O₂ activation under 450 nm light irradiation by rationally modulating the coordination environment of Cu(Ⅰ) ions and incorporating a photoactive Ir(Ⅲ) module into a supramolecular system,leading to efficient C(sp³)−H photo-oxidation of N-aryl tetrahydroisoquinolines.The hexaformyl end-capped fac-Ir(ppy)₃ module (1),the Ir(Ⅲ)-based twin-cavity cage (2),and the supramolecular Cu₂@2 entity—where two Cu(Ⅰ) ions are coordinated within cage 2—were comprehensively characterized using NMR,HR-MS,and X-ray crystallography.The confined cavities of 2 effectively trap Cu(Ⅰ) ions,protecting them from oxidation by O₂.Mechanistic studies reveal that photoinduced singlet oxygen (¹O₂),generated by the fac-Ir(ppy)₃ module,activates Cu(Ⅰ) to generate superoxide radical (O₂•⁻) species.Importantly,the Cu(Ⅰ) redox-active state is regenerated through electron transfer from the photoexcited *Ir(Ⅲ) state to the resulting Cu(Ⅱ) ions.This study introduces a gradual and controlled energy/electron delivery mechanism from Ir(Ⅲ) module to O₂ and the Cu centres,offering an advanced supramolecular strategy for photo-induced O₂ activation in oxidation reactions.展开更多
基金support from the National Natural Science Foundation of China(22171033 and 22477014).
文摘Efficient activation of dioxygen (O₂) under mild and environmentally friendly conditions remains a challenging yet crucial area of research in chemistry.In this study,we present a simple yet effective approach for O₂ activation under 450 nm light irradiation by rationally modulating the coordination environment of Cu(Ⅰ) ions and incorporating a photoactive Ir(Ⅲ) module into a supramolecular system,leading to efficient C(sp³)−H photo-oxidation of N-aryl tetrahydroisoquinolines.The hexaformyl end-capped fac-Ir(ppy)₃ module (1),the Ir(Ⅲ)-based twin-cavity cage (2),and the supramolecular Cu₂@2 entity—where two Cu(Ⅰ) ions are coordinated within cage 2—were comprehensively characterized using NMR,HR-MS,and X-ray crystallography.The confined cavities of 2 effectively trap Cu(Ⅰ) ions,protecting them from oxidation by O₂.Mechanistic studies reveal that photoinduced singlet oxygen (¹O₂),generated by the fac-Ir(ppy)₃ module,activates Cu(Ⅰ) to generate superoxide radical (O₂•⁻) species.Importantly,the Cu(Ⅰ) redox-active state is regenerated through electron transfer from the photoexcited *Ir(Ⅲ) state to the resulting Cu(Ⅱ) ions.This study introduces a gradual and controlled energy/electron delivery mechanism from Ir(Ⅲ) module to O₂ and the Cu centres,offering an advanced supramolecular strategy for photo-induced O₂ activation in oxidation reactions.
