Stacked Reticular Frame Boosted Circularly Polarized Luminescence of Chiral Covalent Organic Frameworks

Abstract Chiral covalent organic frameworks (COFs) with circularly polarized luminescence (CPL) are intriguing as advanced chiroptical materials but have not been reported to date. We constructed chiroptical COF materials with CPL activity through the convenient Knoevenagel condensation of formyl‐functionalized axially chiral linkers and C3‐symmetric 1,3,5‐benzenetriacetonitrile. Remarkably, the as‐prepared chiral COFs showed high absorption and luminescent dissymmetric factors up to 0.02 ( g abs ) and 0.04 ( g lum ), respectively. In contrast, the branched chiral polymers from the same starting monomers were CPL silent. Structural and spectral characterization revealed that the reticular frame was indispensable for CPL generation via confined chirality transfer. Moreover, reticular stacking boosted the CPL performance significantly due to the interlayer restriction of frame. This work demonstrates the first example of a CPL‐active COF and provides insight into CPL generation through covalent reticular chemistry, which will play a constructive role in the future design of high‐performance CPL materials.