Ultrafine Pd Nanoparticles on Triphenylphosphine‐Covalent Organic Framework for Dual Photo/Thermal Catalysis of Scalable C‐C/C‐N Cross‐Couplings

Abstract The development of highly active and reusable heterogeneous catalysts for scalable organic synthesis remains a critical challenge. Here, a covalent organic framework (TyPPc‐COF) with aldehyde residues was synthesized and post‐modified with triphenylphosphine ligands to construct TyPPc‐P‐COF. Subsequently, ultrafine Pd nanoparticles (2.73 nm) were uniformly anchored onto TyPPc‐P‐COF via phosphine‐Pd coordination. The resultant TyPPc‐P@Pd NPs exhibit dual‐mode catalytic functionality: In C‐C cross‐coupling reactions involving aryl iodides, this catalyst demonstrates excellent performance under both thermal catalytic conditions (50 mg catalyst, TOF = 1060 h −1 ) and photocatalytic conditions (30 mg catalyst, TOF = 1780 h −1 ), achieving gram‐scale yields (>80%). Notably, under both photocatalytic and thermal catalytic conditions, this catalyst also efficiently catalyzes Suzuki‐Miyaura, Heck, and Sonogashira C‐C coupling reactions involving aryl bromides and aryl chlorides, which typically exhibit lower activity. Furthermore, it has been demonstrated that light irradiation can effectively extend catalytic functionality to C‐N bond formation. Stability tests revealed negligible Pd leaching/aggregation after multiple cycles, confirming structural robustness. This work provides a general strategy for designing COF@MNPs merging high activity, recyclability, and environmental compatibility, advancing sustainable organic synthesis.