Manipulating Solid-State Intramolecular Motion toward Controlled Fluorescence Patterns

Molecules have limited mobility in the solid state because of the strong intermolecular interactions, and therefore, applications based on solid-state molecular motions are seldom explored. Herein, by manipulating the solid-state intramolecular motion of tetraphenylethylene (TPE) in a crystallizing polymer matrix, controlled fluorescent patterns with information storage and encoding functionality are developed. The intramolecular mobility of TPE can not only affect the fluorescence intensity but also determine the photocyclization activity, which can be tuned by surrounding polymer rigidity. The soft amorphous region in the semicrystalline polymer facilitates the intramolecular motion to achieve weak blue emission and high photocyclization activity, whereas the rigid crystalline phase restricts the intramolecular motion to give intense blue emission and low photoreactivity. Meanwhile, in the process of crystallization, the dynamic movement of the polymer chain in the crystal growth boundary layer further accelerates the intramolecular motions of TPE, allowing enhanced photoreactivity across crystalline and amorphous regions. The motion-dominated fluorescence allows TPE as a smart molecular robot to generate desired fluorescent patterns triggered by polymer crystallization. Our findings provide a correlation between microscopic molecular motions and macroscopic optical signals.