Polymorphism and Light-Driven Forward Movement of TPE Derivative Micro-Crystal due to ArH-pi Interactions Difference.

Aggregation-induced emission (AIE) and aggregation-caused quenching (ACQ) are two classes of opposite luminescence phenomena. It is almost impossible to show both AIE and ACQ effect simultaneously by the same molecule. However, here we report that a simple TPE derivative TAP-TPE grows into both AIE crystals and ACQ ones. It is found that equatorial, contact distance-longer and weak ArH-π interactions exist in AIE crystals while vertical, contact distance-shorter and strong ArH-π interactions appear in ACQ crystals. Theoretical calculation of electron density on the interaction atoms unveils that ACQ crystals have much larger change in electron density than AIE ones, suggesting that the intermolecular electron transfer aroused by the strong ArH-π hydrogen bonds leads to ACQ phenomenon. This result provides a new insight into the emission mechanism in aggregation state. Interestingly, due to the ArH-pi interactions difference, only one of five kinds of crystals shows rapid photochromism, and can act as multimode anti-counterfeiting materials. Very exceptionally, for the first time we find that the photochromic micrometric rod-like crystal even makes forward rolling movement as it repeatedly bends and straightens by responding to on and off of the ultraviolet light irradiation, displaying potential for photo-actuator and light-driven micro-vehicle.