Taming of Triazole, Tetrazole, and Azido Groups: Nitrogen-Rich Energetic Materials with High Thermal Stabilities

Nitrogen-rich energetic materials are of interest due to their potential use as high-energy-density materials in various applications. However, most compounds with a high nitrogen content show poor thermal stabilities, which may limit their use in certain applications. In pursuit of nitrogen-rich energetic materials, this study presents the synthesis and characterization of two nitrogen rich energetic compounds, namely 3-azido-1-(1<i>H</i>-tetrazol-5-yl)-1<i>H</i>-1,2,4-triazol-5-amine (<b>3</b>, C₃H₃N₁₁, N%: 79.78) and (<i>E</i>)-1,2-bis(3-azido-1-(1<i>H</i>-tetrazol-5-yl)-1<i>H</i>-1,2,4-triazol-5-yl) diazene (<b>7</b>, C₆H₂N₂₂, N%: 80.62). Compounds <b>3</b> and <b>7</b> have high thermal stabilities of 216 and 221 °C, respectively, making them the most thermally stable among metal-free primary explosives. Additionally, they show good energetic performance (<i>v</i>_D: 8345 m s^-1; <i>P</i>: 25.17 GPa; <i>v</i>_D: 8275 m s^-1; <i>P</i>: 25.57 GPa), making them potential candidates for metal-free high energy primary explosive. The energetic salts of <b>3</b> and <b>7</b> were also investigated. Among them, hydrazinium salt <b>11</b> displays better energetic performance (<i>v</i>_D: 9089 m s^-1; <i>P</i>: 30.55 GPa), which was on par with those of cyclotetramethylene tetranitramine (HMX). This research contributes to the exploration of nitrogen-rich energetic materials with potential applications in various fields.