Unveiling the Local Structure of Palladium Loaded into Imine‐Linked Layered Covalent Organic Frameworks for Cross‐Coupling Catalysis

Layered covalent organic frameworks (2D‐COFs), composed of reversible imine linkages and accessible pores, offer versatility for chemical modifications towards the development of catalytic materials. Nitrogen‐enriched COFs are good candidates for binding Pd species. Understanding the local structure of reacting Pd sites bonded to the COF pores is key to rationalize interactions between active sites and porous surfaces. By combining advanced synchrotron characterization methods with periodic computational DFT modeling, the precise atomic structure of catalytic Pd sites attached to local defects is resolved within an archetypical imine‐linked 2D‐COF. This material was synthesized using an in situ method as a gel, under which imine hydrolysis and metalation reactions are coupled. Local defects formed in situ within imine‐linked 2D‐COF materials are highly reactive towards Pd metalation, resulting in active materials for Suzuki–Miyaura cross‐coupling reactions.