Chem. Mater., 2017, 29, 5720-6726.

Homochiral porous framework as a platform fordurability enhancement of moleculer catalysts.

Self-quenching and vulnerability ofactive sites are major issues posed for practical applications of highlyefficient chiral organometallic catalysts. Here, we demonstrate an effectivestrategy to address these challenges by constructing them into homochiralporous frameworks, which renders them with extraordinary resistance againstdeactivation yet fully retains the intrinsic catalytic activities and selectivitiesunder heterogeneous systems. Representatively, after partial metalation of theporous chiral phosphoramiditeligand-based frameworks (Phos-HPFs)with Rh species, the afforded catalysts exhibit dramatically enhanceddurability while maintaining the activity and selectivity of the homogeneouscounterparts in asymmetric hydrogenation of olefins. The rigid framework of Phos-HPFscan isolate the active sites, thus preventing the self-quenching from forming coordinativelysaturated complexes, while the active sites surrounded by dense free chiralligands in Phos-HPFscan inhibit them from decomposing into metallic particles. Our work therebyhighlights the advantages of HPFs for the deployment of catalysts, which offersan opportunity for enhancing the utilization efficiency rather than merelyhaving the benefits of easy separation and recycling of the chiral catalysts.