A Nickel Anchored Covalent Organic Framework as Unimolecular Metallaphotocatalyst for Visible Light Driver C−P Bond Coupling Reaction

Abstract The urgent need to develop a sustainable and environmentally friendly method for synthesizing organophosphine compounds is underscored by their extensive applications in organic synthesis, coordination chemistry, medicinal chemistry, and photoelectric materials. Metalated covalent organic frameworks (MCOFs), which seamlessly integrate the inherent photo properties of COF with the catalytic capabilities of metal ions, offer an optimal material for efficient transformation of organics sustainably. In this study, we introduce a simple COF with nickel anchorages (Bpy‐COF‐NiCl 2 ) as a unimolecular metallaphotocatalytic system for effective C−P bond formation. This heterogeneous photocatalyst exhibits superior catalytic performance, achieving yields of up to 95 %, and demonstrates broad substrate tolerance and functional group reactivity. Notably, the metallaphotocatalytic system has demonstrated the capability to process aryl bromides to produce the desired product, a feat not previously reported. Finally, the production and reusability test at the gram scale attests to its superior practicality for designing future organic cross‐coupling reactions.