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

## TL;DR

A new nickel-based catalyst in a metal-organic framework allows chemical reactions to happen in air, making the process more practical and sustainable.

## Contribution

A heterogeneous nickel photocatalyst is developed that enables sulfonylation under ambient air conditions.

## Key findings

- Nickel complexes immobilized in a zirconium-based MOF enable air-insensitive sulfonylation of aryl halides.
- Solvent coordination significantly enhances the catalytic activity of the framework-supported nickel system.
- The system provides insights into designing robust heterogeneous photocatalytic systems for sustainable cross-coupling.

## 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.

Immobilizing a nickel complex coordinated with a specially designed bidentate ligand into a stable zirconium‐based metal–organic framework establishes a heterogeneous platform for promoting air‐insensitive sulfonylation of aryl halides. In this system, solvent coordination is found to enhance C─S bond formation, a process that is challenging to investigate in homogeneous transition‐metal catalysis.