Triphenylphosphine‐Based Covalent Organic Frameworks and Heterogeneous Rh‐P‐COFs Catalysts

The synthesis of phosphine‐based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine‐based COFs (termed P‐COFs) with well‐defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P‐COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance. This work not only extends the phosphine‐based COF family, but also demonstrates their application in immobilizing homogeneous metal‐based (e.g., Rh‐phosphine) catalysts for application in heterogeneous catalysis.