Reconfigurable Visible Light‐Driven Liquid Crystalline Network Showing Off‐Equilibrium Motions Enabled by Mesogen‐Grafted Donor–Acceptor Stenhouse Adducts

Abstract Liquid crystalline network (LCN)–based soft actuators have opened up great opportunities to fabricate emerging and intriguing smart materials, serving as potential building blocks for intelligent soft robotics. Endowing LCN actuators with complex responsive behaviors to enhance their intelligence is both challenging and highly demanded. Herein, Donor–Acceptor Stenhouse Adducts (DASAs) molecules with rod‐like mesogen and the polymerizable group are judiciously designed and synthesized, which is strong‐colored at linear form and de‐coloration at cyclic form after visible light. In the colored state, the DASA presents a striking photothermal effect that is capable of driving the motions of LCN film. Upon visible light irradiation, the DASA becomes colorless, making the diminishing photothermal effect. The light‐gated switching of the photothermal effect renders the LCN films to be reconfigurable and perform off‐equilibrium motions. The varying glass transition temperature of LCN matrix endowing tunable isomerization rates of DASAs and the equilibrium balance of photo‐ and thermal‐isomerization at different temperatures in LCN‐P‐DASA film mainly guiding the off‐equilibrium or stable motions, providing high adjustability of the novel visible light‐driven LCN actuators. The multiply modulated LCN‐P‐DASA film holds great potential in constructing complex visible light‐driven soft actuators based on the synergetic effect and interactions of photochemical and photothermal effects.