Fabrication of Energetic Metal–Organic Frameworks: Potassium 5‑Carboxylato-3,4-Dinitropyrazole and Potassium 5‑(Hydrazinecarbonyl)-3,4-Dinitropyrazole

Energetic materials have been widely applied in civil and military fields, whose thermostability is a key indicator to evaluate their safety levels under severe conditions. Herein, two novel energetic metal–organic frameworks (EMOFs), namely, 4 and 6, were experimentally obtained and comprehensively characterized. The two EMOFs both possess unique three-dimensional (3D) coordination structures. With a high crystal density of 2.184 g·cm–3, EMOF 4 exhibits outstandingly superior thermostability (onset: 290 °C; peak: 303 °C), while EMOF 6 features onset and peak decomposition temperatures of 220 and 230 °C. The calculated energetic parameters of 4 and 6 are as follows: detonation velocity: 8731 m·s–1 and 8294 m·s–1; detonation pressure: 26.5 and 26.4 GPa. Compared to EMOF 6, EMOF 4 features high energy, excellent thermostability, and low mechanical sensitivities, which should be partly attributed to more plentiful coordination interactions. More coordination bonds are conducive to strengthening the EMOF framework, which needs much more energy to collapse, thereby maintaining higher thermal stability. The above favorable characteristics not only indicate EMOF 4 has a promising future in applications as a thermostable explosive but also provide an effective and feasible strategy for developing novel heat-resistant energetic materials via reinforced frame structures of EMOFs