Self‐Healing and Stretchable Molecular Ferroelectrics with High Expandability

The interplay between crystal ordering and stretchability is frequently encountered in contemporary materials science, particularly in the case of ferroelectrics. The inherent dilemma arises when these materials need to withstand repetitive mechanical deformations or stretching without sacrificing their crystal integrity, all while retaining their remarkable ferroelectric properties and even exhibiting self‐healing capabilities. This complexity further presents a significant challenge in the design and engineering of mechanically rigid molecular ferroelectric crystals, particularly for applications where both precise crystalline structure and mechanical adaptability are crucial. In this study, the humidity‐controlled expansion and contraction, dissolution, and recrystallization of a self‐assembled molecular ferroelectric‐in‐hydrogel framework are reported. Self‐healing ferroelectric‐in‐hydrogel networks exhibit a recyclable humidity‐tailored ionic conductivity from 2.86 × 10−6 to 1.36 × 10−5 S cm−1, facilitating the stretchable piezoelectric sensing. Additionally, the dynamic bond reforming interactions are observed, leading to the tailoring of Young's modulus from 452 to 170 MPa, maintaining ferroelectricity under a strain of 20% with a piezoelectric coefficient of 15.7 pC N−1. Upon lattice contraction, the molecular contacts undergo reforming, leading to the restoration of stretchable ferroelectrics/piezoelectrics and paving the way for stretchable bioelectronics for full‐body motion monitoring. The capabilities highlighted here open avenues for stretchable and self‐healing ferroelectric‐in‐hydrogel bioelectronic technologies.