Construction of High-Performance Energetic MOFs: C4N8O42– and C3N4O42– with Their Derivatives, Compared with Their Energetic Salts

A promising strategy for handling the inherent contradiction of energetic materials (EMs, energy vs stability) of energetic metal–organic frameworks and energetic salts is proposed. A series of novel high-performance EMs, energetic metal–organic frameworks of [(C 4 N 8 O 4 2– )(K + ) 2 (H 2 O) 2 ], [(C 3 N 4 O 4 2– ) 2 (Cu 2+ ) 2 (H 2 O) 4 ], [(C 4 HN 8 O 4 – )(K + )(H 2 O)] and [(C 4 HN 8 O 4 – ) (K + )(H 2 O)] ( 2 – 3 and 5 – 6 ) and energetic salts of 7 – 11, were synthesized, characterized, and fully investigated. The detailed structures and physiochemical properties of 2 – 3 and 5 – 8 were obtained by single-crystal X-ray diffraction (XRD). Differential scanning calorimetry, impact sensitivity, and friction sensitivity were measured followed by the simulation and calculation of the Δ H f, noncovalent interaction, detonation velocity and pressure, and Hirshfeld surface to evaluate the comprehensive physiochemical properties of the synthesized substances. The relationships between the thermal stabilities, mechanical sensitivities, and detonation performance with molecular structures of the compounds were fully discussed. Additionally, the reaction transition states and bond dissociation energy of nitro were simulated to investigate the reaction mechanism of the preparation and decomposition of 2 for future studies on EMs.