Zipper‐Like Dynamic Switching of Coordination Bonds Gives a Polar Bimetallic Halide Toward Self‐Driven X‐Ray Detection

Abstract Polar molecular crystals hold a promise for controlling bulk physical properties originated in their unique switchable polarity via structural transformation. However, the mechanisms for switching polarization are mainly limited to displacive and disorder‐order phase transitions, which rarely involve the reconstruction of chemical bonds. Here, we have switched and tuned electric polarization in a bimetallic halide, (Neopentylammonium) 4 AgBiBr 8 ( 1 ), as verified by light‐excited pyroelectric effect. Most notably, its Ag−Br coordination bonds show a zipper‐like dynamic switching behavior from the ‘locked’ to ‘unlocked’ state, namely, reconstruction of chemical bonds. Coupling with the dynamic ordering of organic cations, this bond‐switching transition makes a contribution to switchable polarization of 1 . As expected, its polarity creates pyroelectric effect for self‐driven X‐ray detection with high sensitivity (3.8×10 3 μC Gy −1 cm −2 ) and low limit of detection (4.8 nGy s −1 ). This work on the bond‐switching mechanism provides an avenue to design polar molecular candidate for smart optoelectronic devices.