Supramolecular Chalcogen‐Bonded Shape Memory Actuators

Abstract Supramolecular liquid crystal elastomers (LCEs) incorporating chalcogen bonds (ChBs) have been synthesized and investigated for shape memory and actuation properties. LCEs featuring strong Se⋯N ChBs (−40 to −43 kJ mol −1 ) exhibit both shape memory effects (SME) and reversible actuation, while those with weaker S⋯N ChBs (−32 to −34 kJ mol −1 ) do not. The Se⋯N‐based LCEs transition from one‐way to two‐way SME after three days at room temperature, enabling programmable 2D/3D shape transformations and rewritable surface patterns. They also enable the fabrication of light‐powered crawling robots as well as temperature‐responsive knot‐like actuators. These results highlight the critical role of the ChB strength and specificity in designing functional materials. Solid‐state NMR, Raman spectroscopy, and density functional theory calculations provide further molecular‐level insights into ChB interactions, laying the groundwork for advanced supramolecular actuators and shape‐morphing LCEs.