Light‐Up Fluorescence and Circularly Polarized Luminescence in Achiral Interlocked Framework via Adaptive Lone Pair‐π Interaction Confinement

Abstract Interactions between lone pairs and aromatic π systems are significant across biology and self‐assembled materials. Herein, employing an achiral confinement metal–organic framework (MOF) encapsulates guest molecules, it is successfully realized that lone pair (lp)‐π interaction induces fluorescence “turn‐on” and circularly polarized luminescence for the first time. The MOFs synthesized based on naphthalenediimide show nearly non‐emissive, which can be light‐up by introducing acetone or ester guests containing lone pairs‐π interaction. Furthermore, the introduction of a series of lp‐rich chiral esters induces supramolecular chirality as well as circularly polarized luminescence in achiral MOFs, while also observing chiral adaptability. This work first demonstrates the luminescence and chiral induction via lone pair electrons‐π interactions, presenting a fresh paradigm for the advancement of chiroptical materials.