Dihydrogen Bond Cooperativity Resolves Zero‐Linear Compressibility in an Energetic Crystal

ABSTRACT Zero linear compressibility (ZLC) energetic materials can be used as anti‐shock materials to maintain stability in at high‐pressure environments up to tens of gigapascals under shock conditions. Achieving an energetic material with ZLC properties and clarifying its structure–activity relationship should meet the urgent safety demands. In this study, the first ZLC organic molecular crystal, trimethylamine borane (TMAB), which can be utilized as a propellant component, was discovered. TMAB underwent an isostructural phase transition at 9.2 GPa, as evidenced by the combination of Raman, infrared, and UV–vis absorption spectra and in situ synchrotron x‐ray diffraction patterns. Note that the c axis exhibited intriguing ZLC in the pressure range from 9.2 to 14.0 GPa, indicating the superior stability of TMAB under extreme high pressure. The dihydrogen‐bonding cooperativity effect under high pressure was responsible for the observed ZLC in TMAB, unlike that observed for previously reported ZLC materials. This study developed a ZLC energetic organic molecular crystal and revealed its underlying mechanism, which facilitates the design of anti‐shock propellants.