A Modularly Integrated Chiral Cavitand

Abstract Rational assembly of multiple molecular building blocks enables functional integration. However, precise construction of complex systems comprising of three or more molecular modules is challenging due to the pathway complexity. Here, we report a highly modular, three‐component coassembly system that achieves high‐fidelity integration of chiral functions on a cavitand. The resorcin[4]arene‐derived cavitand, embedded with a sequential hydrogen bonding donor–acceptor array of benzimidazoles, enables corral encapsulation of chiral carboxylic acids and alcohols, promoting the deracemization of the corrals with propeller chirality. This approach allows for the unprecedented construction of modular supramolecular‐chiral cavitand. After installing chiral acid module on corral, the cavity is expanded that could further include a guest molecule as a third module. Chirality was successfully transferred from the cavitand to the luminescent module, resulting in efficient circularly polarized luminescence. This study leverages the propeller chirality of deep cavitands to construct a highly modular, functionally integrated molecular system, demonstrating great potential for building customizable and disassemblable molecular functional platforms.