Visible‐Light‐Actuated Bidirectional Photochromism in Chiral Nanostructures with Multi‐Degree of Freedom

Abstract Cholesteric liquid crystals (CLCs) with chiral nanostructures take on great significance in light modulation for optical devices, especially involving the features of circularly polarized and dynamic structural colors. However, on‐demand self‐assembly by photoprogramming still remains a challenge that is ascribed to the unpredictable variation of the helical superstructures in the existing CLCs induced by light‐driven chiral switches. Here, novel binary chiral systems are designed to construct visible‐light‐actuated CLCs with multi‐degrees of freedom, including adjustable circular polarization, bidirectional photochromism, and manipulable photonic bands. Such systems consist of an o ‐fluoroazobenzene‐containing chiral switch and an inert chiral dopant, whose interaction dominates the strategies of chiral cooperation or conflict to determine the CLC handedness as well as shift direction of the selective reflection. Particularly, the precise tuning range of the structural color is tailored by programmable helical twisting power to enable diverse paradigms of light‐actuated patterning. The unprecedented quantitative manipulation of circularly polarized structural colors offers unique photonic attributes for applications in information encoding and multiplexed communication.