Hierarchical Chiral Luminescent Macrocyclic Porous Organic Polymer from Chiral π‑Conjugated Macrocycles: Tunable Circularly Polarized Luminescence and Enantiomeric Fluorescent Sensing

Chiral molecules and materials have attracted tremendous research interest owing to their intriguing chiral structure and promising applications, whereas precise and modular construction toward chiral structures and frameworks is the cornerstone for their development. Herein, a modular synthetic method toward chiral π-conjugated macrocycles (CCMs) incorporating a well-defined helical tetraarylethene (TAE) moiety is established, which can feasibly afford chiral porous organic polymers (POPs) with mirror-imaged chirality and a hierarchical porous structure via Yamamoto polymerization. These chiral macrocyclic molecules and chiral macrocyclic POPs all show bright emission in solid states owing to the aggregation-induced emission property of the TAE units and exhibit mirror-imaged circularly polarized luminescence (CPL) with a luminescence asymmetric factor on the level of 10–3. Accommodation of rhodamine B as guest molecules into chiral POPs has contributed to color-tunable CPL-active materials owing to chirality transfer and energy transfer from chiral porous polymers to nonchiral guest dyes. The chiral luminescent POPs are further utilized to detect explosive molecules via fluorescent quenching and display enantioselective sensing of chiral nitroaromatics. These results have provided a reliable protocol for developing luminescent chiral porous materials and will further spur the applications of chiral luminescent polymers.