Patternable Shape‐Morphing and Actuation Enabled by Coupling Photo‐ and Thermo‐Programming of Poly(Disulfide)‐Based Liquid Crystalline Elastomers

ABSTRACT The incorporation of dynamic covalent bonds into liquid crystalline elastomers (LCEs) has enabled reprogrammable shape‐morphing capabilities. However, conventional programming stimuli—light and heat—individually exhibit inherent limitations in fabricating geometrically complex, high‐fidelity architectures. Herein, we develop a novel poly(disulfide)‐based LCE (PDS‐LCE) synthesized via end‐capping of liquid crystalline oligomers with 1,2‐dithiolane, followed by crosslinking through ring‐opening polymerization. Leveraging the dual thermo‐ and photo‐responsiveness of the poly(disulfide) segments, the resulting material can be programmed using either stimulus. Thermo‐programming ensures robust and uniform alignment over large areas, whereas photo‐programming provides high spatial resolution, remote, and noncontact patterning with localized precision. By synergistically integrating these two complementary approaches, we achieve sophisticated, reconfigurable, and hierarchically structured LCEs that are unattainable by single‐stimulus programming. Moreover, the dynamic poly(disulfide) network endows the material with self‐healing capability and closed‐loop recyclability. We further demonstrate functional soft robotic applications, including self‐sustained oscillation and light‐guided directional locomotion. This work establishes a versatile platform for designing recyclable and structurally programmable LCEs with advanced functionalities for future soft robotics and adaptive systems.