Air‐Insensitive Sulfonylation Enabled by a MOF‐Supported Nickel Photocatalyst

Abstract Photoredox nickel dual catalysis has become a powerful tool in organic synthesis over the past decade, demonstrating versatile reactivity and utilizing earth‐abundant metals to form new bonds. However, the requirement for strict inert‐gas protection and the existence of intricate metal complex equilibria in homogeneous systems present obstacles to further advancement in practical applications and mechanistic studies. Herein, a heterogeneous strategy is devised by immobilizing nickel complexes within a highly crystalline mesoporous framework, enabling the photoinduced sulfonylation of aryl halides to proceed under ambient air conditions. Notably, pre‐treatment with coordinating solvents significantly enhances the activity of the framework‐supported nickel catalyst. This research not only broadens the scope of sustainable cross‐coupling methodologies but also provides valuable insights into designing robust heterogeneous photocatalytic systems.