Controllable Chiral Self-sorting and Guest Recognition of Ultra-stable Axially Chiral Porous Aromatic Cages

Abstract The synthesis of ultra-stable chiral porous organic cages (POCs) and their controllable chiral self-sorting at the molecular and supramolecular level is still a daunting challenge. Herein, we report the design and synthesis of a serial of axially chiral porous aromatic cages (1-S and 1-R) with exceptional chemical stability. The theoretical and experimental studies on chiral self-sorting reveal that the exclusive self-recognition on cage formation is an enthalpy-driven process while the chiral narcissistic and social self-sorting on supramolecular assembly of racemic cages can be precisely regulated by π–π and C–H…π interactions from different solvents. Moreover, the crystallinity of 1 can be preserved under various harsh conditions including boiling water, and high-concentrated acid and alkali solutions. Further investigations on chiral sensing show that 1 possesses high enantioselectivity toward axially chiral aromatic racemates.