Phosphine-Built-in Porous Organic Cage for Stabilization and Boosting the Catalytic Performance of Palladium Nanoparticles in Cross-Coupling of Aryl Halides.

Herein, we report first a novel phosphine-containing porous organic cage (PPOC) from a [2 + 3] self-assembly of triphenyl phosphine-based trialdehyde and (S,S)-1,2-diaminocyclohexane via dynamic imine chemistry, which was employed as a porous material for the controlled growth of palladium nanoparticles (NPs) due to the strong affinity of Pd to the phosphine ligand based on the principle of hard and soft acids and bases. Comprehensive characterizations including X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, NMR, and X-ray absorption spectroscopy reveal that ultrafine Pd NPs with narrow size distribution (1.7 ± 0.3 nm) and enhanced surface electronic density via a strong interaction between NPs and phosphine were homogeneously dispersed in the PPOC. The resultant catalyst Pd@PPOC exhibits remarkably superior catalytic activities for various cross-coupling reactions of aryl halides, for example, Sonogashira, Suzuki, Heck, and carbonylation. The catalytic activity of Pd@PPOC outperforms the state-of-the-art Pd complexes and other Pd NPs supported on N-containing porous cages under identical conditions, owing to the enhanced surface electronic density of Pd NPs and their high stability and dispersibility in solution. More importantly, Pd@PPOC is highly stable and easily recycled and reused without loss of their catalytic activity. This work provides a new functional POC with extended potentials in catalysis and material science.