From Photochromism to Nanoscopy: The Emerging Role of Fluorescent Diarylethene Photoswitches in Super‐Resolution Imaging

Super‐resolution imaging (SRI) achieves nanoscale biological visualization by precisely controlling fluorophore emission over time, a strategy known as “trading time for space”. Fluorescent diarylethene (DAE) photoswitches, with exceptional reversibility, thermal stability, fatigue resistance, and tunable photochromism, enable this approach by reversible switching between fluorescent “on” and dark “off” states, allowing neighboring molecules within the diffraction limit to be distinguished. Fluorescent DAE derivatives have recently garnered increasing attention as fluorescent labels for SRI applications, offering decisive advantages over conventional photoswitches. Despite considerable progress, a systematic review specifically addressing the application of DAEs in SRI remains absent. Herein, we present a comprehensive survey of fluorescent DAE photoswitches for SRI, centering on molecular design strategies and recent advances. We categorize these systems into four classes based on their activation modes and driving mechanisms: “turn‐on” fluorescent DAEs, “turn‐off” fluorescent DAEs, polymeric fluorescent DAEs, and visible‐light‐driven DAEs. For each category, we highlight representative structures, key design rationales, and imaging performance benchmarks. We conclude by identifying current challenges and outlining future perspectives, aiming to guide the rational development of next‐generation fluorescent DAE photoswitches for advanced super‐resolution bioimaging.