All‐Visible‐Light Diarylethene Photoswitches and Control over Dynamic Conjugate Addition Reactions

All‐visible‐light‐driven photoswitches are gaining significant attention for their environmental friendliness and biocompatibility. Here, a series of visible‐light responsive photoswitches is presented by embedding α,β‐unsaturated 1,3‐dicarbonyl motifs into the ethene bridge of dithienylethene (DTE) scaffolds. Through electronic modulation and π‐conjugation extension, the absorption is redshifted into the visible range, enabling reversible photochromic ring‐closure and ring‐opening under blue and red light, respectively. Density functional theory calculations reveal that electron‐withdrawing groups and extended conjugation narrow the HOMO–LUMO gap, enhancing photoswitching efficiency. Furthermore, these photoswitches also function as dynamic Michael acceptors, allowing visible‐light‐controlled CS bond formation and cleavage with great reversibility. The work described offers a versatile platform for visible‐light‐regulated dynamic covalent chemistry and paves the way for the development of recyclable, biocompatible materials.