Spatially Decoupled Main‐Chain/Side‐Chain Cholesteric Liquid Crystal Elastomers for Synchronized Color‐Shape Responses

ABSTRACT Cholesteric liquid crystal elastomers (CLCEs) combine structural color with mechanical actuation, making them attractive for adaptive photonic materials, soft robotics, and bioinspired camouflage. However, broad thermochromism and efficient mechano‐actuation usually rely on incompatible molecular architectures: side‐chain CLCEs favor thermal pitch tunability, whereas main‐chain systems enable effective stress transfer and shape‐memory actuation. Integrating these responses into a single material therefore remains challenging because the molecular requirements for color tuning and anisotropic deformation inherently compete. Here, we report a spatially decoupled yet topologically unified main‐chain/side‐chain CLCE network that integrates these functions while minimizing mutual interference between their response pathways. In this architecture, side‐chain mesogens remain responsible for thermally driven pitch modulation and thermochromism, whereas main‐chain liquid‐crystalline segments mediate anisotropic stress transfer, mechanochromism, and shape‐memory actuation. By precisely tuning network topology, crosslinking density, and chiral composition, we align these independently optimized response modes within a common stimulus window. The resulting freestanding elastomers exhibit a 165 nm thermochromic window, a 240 nm mechanochromic range, high mechanical robustness, and programmable two‐way shape memory, enabling synchronized color–shape evolution, reconfigurable information encryption, and biomimetic adaptive camouflage. This work establishes a general strategy for integrating differentiated yet cooperatively operating molecular functions into soft photonic materials.