Photoactivation of Millimeters Thick Liquid Crystal Elastomers with Broadband Visible Light Using Donor–Acceptor Stenhouse Adducts

Abstract Light‐responsive liquid crystal elastomers (LCEs) are stimuli‐responsive materials that facilitate the conversion of light energy into a mechanical response. In this work, a novel polysiloxane‐based LCE with donor–acceptor Stenhouse adduct (DASA) side‐chains is synthesized using a late‐stage functionalization strategy. It is demonstrated that this approach does not compromise the molecular alignment observed in the traditional Finkelmann method. This easy, single‐batch process provides a robust platform to access well‐aligned, light‐responsive LCE films with thickness ranging from 400 µm to a 14‐layer stack that is 5 mm thick. Upon irradiation with low‐intensity broadband visible light (100–200 mW cm⁻²), these systems undergo 2D planar actuation and complete bleaching. Conversely, exposure to higher‐intensity visible light induces bending followed by contraction (300 mW cm⁻²). These processes are repeatable over several cycles. Finally, it is demonstrated how light intensity and the resulting heat generation influences the photothermal stationary state equilibrium of DASA, thereby controlling its photoresponsive properties. This work establishes the groundwork for advancement of LCE‐based actuators beyond thin film and UV‐light reliant systems.