Rewritable, Stable, and Precise Optical Printing on Organohydrogel via Confining Dynamic Covalent Bond Exchange Between Crystalline Microdomains

Abstract

ABSTRACT Optical printing on soft materials offers significant advantages for spatiotemporally controlled patterning in adaptive optics, information encryption, and reconfigurable devices. However, current strategies face challenges in achieving precise and rewritable pattern control with long‐term stability due to uncontrolled diffusion kinetics of reactive species and structural instability upon stimulus removal. Here, we design a crystal‐restricted dynamic organohydrogel that achieves precise optical patterning via confining dynamic covalent bond exchange between crystalline microdomains. These microdomains act as physical boundaries that restrict bond exchange and migration to microscale spaces, thereby accelerating exchange kinetics and network rearrangement for precise optical printing. Moreover, crystalline microdomains provide higher energy barriers that ensure long‐term pattern stability through shape retention below crystallization temperature, maintaining pattern fidelity for over 180 days. The system demonstrates exceptional shape memory performance with 98% fixity and recovery ratios over 20 cycles. Additionally, reversible phase transitions coupled with dynamic bond exchange enable rapid self‐healing and rewritable optical printing for information encoding, encryption, and controlled erasure. This design principle can be extended to other dynamic polymer systems, offering a generalizable platform for intelligent responsive interfaces with potential applications in anti‐counterfeiting and adaptive mechanical devices.