Revealing Concentration-Dependent Amplification and Inversion of Circularly Polarized Luminescence in Liquid Crystal Self-Assemblies.

Elucidating supramolecular chiral evolution remains challenging, owing to weak chiroptical signals and poorly characterized conformationally diverse chiral dimers. Here, we adopt liquid crystal matrices to amplify chiroptical signals for real-time monitoring of monomer-to-aggregate chiral evolution. In this pyrene-based supramolecular system, π-π stacking and C-H···π interactions drive the formation of discrete dimers within nematic liquid crystals. The significantly amplified CPL signals with glum values up to 10-1 enable direct visualization of chiral transformation. Structural analyses verify that offset face-to-face dimers possess reversed handedness relative to monomers, thus inducing chiroptical inversion. TCNB allosteric encapsulation induces spatial rearrangement of BP dimers within liquid crystal and modulates their helicity-dependent chiroptical activity. A maximum glum value of 0.97 is achieved at the bandgap edge. Such structure reshaping confirms that assembly concentration regulation and molecular intervention enable precise engineering of chiral aggregates, offering fundamental insights into chiral evolution in supramolecular assembly systems.