Abnormal Slow Phonon Dynamics Toward Prolonging Excited States Dynamics Enabled by Crystalline‐Assembling Donor–Acceptor Molecules

Abstract Phonon dynamics are a critical factor to control the optical properties of excited states in light‐emitting materials. Here, we report an extremely slow relaxation of photoexcited lattice vibrations enabled by assembling the donor‐acceptor (D–A) molecules [2‐(9,9‐dimethylacridin‐10(9H)‐yl)‐9,9‐dimethyl‐9H‐thioxanthene 10,10‐dioxide], namely AC molecules, into dipolar crystal. By using photoexcitation‐modulated Raman spectroscopy, we find that the crystalline‐lattice vibrations monitored by Raman‐scattering laser beam of 785 nm demonstrate an un‐usual slow relaxation in the time scale of seconds after ceasing photoexcitation beam of 343 nm in such dipolar crystal. This presents extremely slow phonon dynamics enabled by crystalline‐assembling the D–A molecules into a dipolar crystal. Simultaneously, the photoluminescence (PL) exhibits a prolonged behavior, lasting 10 ms after ceasing photoexcitation in dipolar AC crystal. This phenomenon provides an experimental hypothesis that the slow phonon dynamics function as an important mechanism to unusually prolong excited states dynamics upon crystalline‐assembling the D–A molecules into dipolar crystal. This hypothesis can be verified by directly suppressing the phonon dynamics through freezing D–A molecular liquid into dipolar crystalline solid at 77 K to largely prolong the PL to 1 s‐ after removing photoexcitation. Clearly, crystalline‐assembling D–A molecules provide the necessary conditions to enable slow phonon dynamics toward prolonging excited states dynamics.