Visible‐Light‐Triggered Carbene Crosslinking in Dynamic Disulfide Networks for Patternable, Debondable, and Recyclable Smart Adhesives

Smart pressure‐sensitive adhesives (PSAs) capable of on‐demand debonding and recycling are highly desirable for advancing the sustainability of flexible electronics and devices. Here, we report a visible‐light‐responsive PSA based on a dynamic copolymer composed of α‐thioctic acid (TA) and a diazo‐functionalized acrylate. The dynamic disulfide backbone imparts intrinsic self‐adhesion and closed‐loop recyclability, while the diazo moieties enable ultrafast carbene‐mediated crosslinking upon blue light (420 nm) irradiation. This rapid crosslinking triggers a synergistic effect within 10 s: it elevates the bulk modulus of the adhesive matrix to facilitate ultrafast interfacial debonding, while the concurrent in situ evolution of N 2 creates a microporous architecture that enables high‐resolution surface patterning. Moreover, the resulting hierarchical porosity dramatically accelerates ethanol infiltration, driving rapid removal of the patterned area, thereby enabling selective recyclability of the unexposed polymer. Consequently, this work establishes a versatile and sustainable paradigm for smart adhesives, seamlessly integrating, on‐demand debonding and recyclability for next‐generation flexible electronics.