Conformation‐Resolved Single‐Luminogen Systems for Time‐Dependent Multicolor Afterglow

ABSTRACT Time‐dependent multicolor afterglow enables temporal encoding of naked‐eye distinguishable optical signals that cannot be achieved with static luminescence. However, available strategies to control the wavelength and color of time‐dependent multicolor afterglow remain highly limited. Herein, we propose a conformation‐resolved molecular design that successfully unlocks intrinsic dual‐phosphorescence characteristics in single‐luminogen systems, enabling dynamically color‐tunable afterglow within the polymer matrix. Our strategy integrates flexible C–S–C rotors into a rigid pyrene core, allowing simultaneous stabilization of distinct emissive conformers with different triplet energy levels, specifically, a parallel conformer that can produce red phosphorescence and a perpendicular one yielding green phosphorescence. The asynchronous decay of these phosphorescent afterglows results in a visually perceptible emission color transition from red to yellow, and finally to green over a naked‐eye distinguishable time scale, representing a rare paradigm of intrinsic, conformation‐mediated dual‐phosphorescence. Moreover, our systems are able to exhibit remarkable resistance to water, acids/bases, and organic solvents, as well as intrinsic UV‐shielding capabilities, demonstrating that the time‐dependent multicolor afterglow can readily integrate with diverse material functionalities, and is thus well suited for a wide range of application scenarios.