This work presents a versatile strategy to fabricate nanointerfacial-slipping-restricted photoactuation elastomers by chemically bonding the nanofillers into a thermally actuatable liquid crystal network for long-term stable cycling photoactuation.

Photoswitchable fluorescent materials have gained significant attention for their potential in advanced information encryption and anti‐counterfeiting applications. However, the common use of UV light to trigger the isomerization processes leads to photobleaching and poor fatigue resistance. Visible‐light‐driven fluorescent photoswitches are highly desirable, but achieving high cyclization yield remains challenging. Herein, it is reported that all visible‐light‐driven turn‐on fluorescence in dimethoxyphenyl functionalized diarylethene isomers. The open‐ring form of o‐DMPB and p‐DMPB exhibits near quantitative conversion yields (up to 94%) under 405 nm visible light, attributed to the strong electron‐donating character. In contrast, the meta isomer m‐DMPB shows limited response to visible light, with a ring‐closing yield of 22%. Furthermore, all photoswitches display good thermal stability, photostability, and fatigue resistance. Notably, o‐DMPB demonstrates promising applications in anti‐counterfeiting, information encryption, and photorewritable patterns. This work provides a valuable strategy for the development of high‐performance fluorescent photoswitches.

Diarylethenes (DAEs) are typical photochemically reversible type (P‐type) photochromic materials with excellent thermal stability and high fatigue resistance and are widely exploited as photo‐switches for various applications in molecular devices, data storage, photoresponsive materials, and bioimaging, etc. In recent years, there is an increasing number of reports using heat, acid, electrochemistry, etc. to drive the isomerization reaction of DAEs. The response to two or more different stimuli enables multi‐functionality within a single DAE molecule, which would facilitate complex logic‐gate operations, multimode data storage, and increased information density. Herein, the recent advances in DAE systems utilizing stimuli “beyond photo” to trigger the isomerization processes from three perspectives: acidochromism, thermochromism, and electrochromism are reviewed. Emphasis is placed on the molecule design strategies and the underlying mechanisms for cyclization and cycloreversion processes addressed by the alternative stimulus. Then the noticeable applications made in multi‐stimuli responsive DAE systems are summarized. Additionally, the challenges and opportunities of DAE switches driven by stimuli “beyond photo” in the future are also discussed.