Precisely Defining Local Gradients of Stimuli‐Responsive Hydrogels for Complex 2D‐to‐4D Shape Evolutions

Abstract The intellectualization and complication of existing self‐shaping materials are limited by the inseparable monotonic relationship between their deformation rate and deformation degree (i.e., a higher deformation rate is accompanied by a high deformation degree). This causes that they can only deform from 2D to 3D states. Here, a simple yet versatile strategy to decouple the monotonic correlation between the deformation rate and deformation degree of self‐shaping hydrogels is presented for achieving complex deformations from 2D to temporary 3D to 3D (2D‐to‐4D). It is demonstrated that when the gradient hydrogels prepared by photopolymerization possess dense polymer networks, the local regions with a high deformation rate can exhibit a low deformation degree. The resulting hydrogels can thus deform in a novel 2D‐to‐4D mode under external stimuli. During the deformation, they first transform into the temporary shapes induced by the local deformation rate difference, and then transform into the final shapes determined by the local deformation degree difference. Through controlling the ultraviolet irradiation direction and time to precisely program the local gradients of self‐shaping hydrogels, they can be designed to produce various unprecedented yet controllable 2D‐to‐4D shape evolutions on demand, such as transformable origami, sequential gesture actions in finger‐guessing games, mobile octopuses, time switch, etc.