Tricolor Luminescence Switching by Thermal and Mechanical Stimuli in the Crystal Polymorphs of Pyridyl‐substituted Fluorene

Stimuli‐responsive organic luminescence‐switching materials have attracted much attention for a decade. Most of the reported examples display a reversible two‐color luminescence switching, and multicolor‐switching materials remain extremely rare. Herein, we report a simple organic molecule, 4,4′‐(9,9‐dimethyl‐9H‐fluorene‐2,7‐diyl)dipyridine (MFDP), which exhibits three different crystal polymorphs (V‐MFDP, B‐MFDP and G‐MFDP) with different luminescent colors. Furthermore, the three crystal polymorphs show a reversible tricolor fluorescent switching from violet to blue and to green upon physical stimuli. The single‐crystal structures of the three polymorphs were obtained, and the results indicate that the stimuli‐responsive properties of the three polymorphs come from the different stacking modes induced by intermolecular interactions. The competition between weak π–π stacking and weak hydrogen bonding is the main reason for the the phase transformations among the three crystal polymorphs. Tricolor neons: A fluorene‐based functional molecule is reported which exhibits three different crystal polymorphs with different luminescent colors. The tricolor luminescence can be reversibly switched by thermal and mechanical stimuli. The crystal structures revealed the mechanism of the phase transformation and luminescence switching.