Silver(I)-Based Molecular Perovskite Energetic Compounds with Exceptional Thermal Stability and Energetic Performance

In recent years, molecular perovskite energetic materials have attracted more attention because of their simple synthesis processes, high thermal stabilities, excellent performances, and great significance as a design platform for energetic materials. To explore the possibility of the application of molecular perovskite energetic materials in heat-resistant explosives, four silver(I)-based molecular perovskite energetic compounds, (H₂A)[Ag(ClO₄)₃], where H₂A = piperazine-1,4-diium (H₂pz²⁺) for PAP-5, 1-methyl-piperazine-1,4-diium (H₂mpz²⁺) for PAP-M5, homopiperazine-1,4-diium (H₂hpz²⁺) for PAP-H5, and 1,4-diazabicyclo[2.2.2]octane-1,4-diium (H₂dabco²⁺) for DAP-5, were synthesized by a one-pot self-assembly strategy and structurally characterized. The single-crystal structures indicated that PAP-5, PAP-M5, and DAP-5 possess cubic perovskite structures while PAP-H5 possesses a hexagonal perovskite structure. Differential thermal analyses showed that their onset decomposition temperatures are >308.3 °C. For PAP-5 and DAP-5, they have not only exceptional calculated detonation parameters (D values of 8.961 and 8.534 km s⁻¹ and P values of 42.4 and 37.9 GPa, respectively) but also the proper mechanical sensitivity (impact sensitivities of ≤10 J for PAP-5 and 3 J for DAP-5 and friction sensitivities of ≤5N for both PAP-5 and DAP-5) and thus are of interest as potential heat-resistant primary explosive components.