Reversible Circularly Polarized Luminescence Inversion and Tunable Emission in Chloride‐Bridge‐Linked Supramolecular Polymers

Achieving precise control over chirality evolution in supramolecular polymers that exhibit circularly polarized luminescence (CPL) inversion during aggregation remains a critical yet challenging endeavor. Herein, the construction of coordinated supramolecular polymers derived from homochiral dimers of four Schiff base derivatives and Zn(II) ions, assembled via dynamic chloride bridges is reported. These supramolecular systems exhibit multiple chiroptical inversions in their aggregated states upon exposure to xylene isomers, a process facilitated by solvent‐induced dimer rotation and reversible dissociation of the chloride bridges. Single‐crystal X‐ray diffraction (SCXRD) analysis reveals that xylene isomers act as molecular actuators, triggering rotational motion of the dimers within the assemblies through hydrogen bonding and C─H···π interactions. By modulating the type of xylene isomer and applying thermal stimuli, precise control over both the CPL inversion and emissive wavelength of these coordinated supramolecular polymers is achieved. This work demonstrates precise control over the chiroptical properties of coordinated supramolecular materials, offering a promising platform for the development of stimuli‐responsive CPL‐active systems with dynamically tunable chirality, particularly for applications in information storage and encryption.