Dynamic coordination and reconstruction-induced chemiluminescence in chiral covalent organic frameworks for enantioselective sensing.

Integrating recognition and signal output into chiral covalent organic frameworks (CCOFs) remains challenging because conventional frameworks are static, with recognition events decoupled from signal transduction. Herein, we report a dynamic coordination strategy to construct chiral covalent organic frameworks (CCOFs) that enable a recognition-triggered reconstruction and reconstruction-induced chemiluminescence (CL) response. Chirality was imparted to an achiral bipyridine-based COF through reversible coordination of enantiopure cysteine (Cys) to framework-mounted cobalt centers, yielding l/d-Cys@Co-TFB-DABP. This design established a competitive ligand displacement mechanism, wherein enantiomer recognition selectively displaces coordinated Cys and triggers in situ reconstruction of the catalytic interface. Such reconstruction then amplifies enantiomer-discriminable CL signals by differentially regulating reactive oxygen species generation, with l-Cys@Co-TFB-DABP producing both ˙OH and 1O2, whereas d-Cys@Co-TFB-DABP produces exclusively ˙OH. The platform exhibited outstanding enantioselectivity toward ibuprofen (slope difference ∼24-fold) and reliably discriminated other chiral analytes, including duloxetine and various amino acids. By integrating recognition, structural modulation, and signal transduction within a single dynamic CCOF, this work established a new strategy for intelligent chiral sensing based on dynamic coordination chemistry, overcoming the long-standing challenge of static frameworks and decoupled functionality.