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

Abstract

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.

Periodate-based molecular perovskites as promising energetic biocidal agents

“…For instance, by changing the A-site components from H 2 dabco 2+ to other organic cations with trimmed C and H atoms or adding O atoms, the oxygen balance parameter and detonation performances could be improved [29,30]. By using silver(I) ions or derivatives of NH ) to serve as the B-site cation, we attained four new silver(I) perchlorate perovskites as potential heat-resistant primary explosives [31] and two metal-free hexagonal perovskite energetic crystals with detonation performances surpassing DAP-4 [32]. Very recently, by using nitrate ions as the X-site bridges, we obtained a nitratebased energetic molecular perovskite as a modern edition of black powder with promising application potentials in the field of gunpowder and pyrotechnics [33].…”

Research progress of EMOFs-based burning rate catalysts for solid propellants

“…Preliminary experimental results showed that (C 6 H 14 N 2 )NH 4 (ClO 4 ) 3 (DAP-4) in molecular perovskite-type energetic materials had a significant catalytic effect on the burning rate of composite modified double-base propellant. In the pressure range of 1–22 MPa, the burning rate at different pressures was basically increased, especially at high pressure (10–22 MPa), the burning rate was greatly increased ( Shang et al, 2022 ; Shang et al, 2020a ; Shang et al, 2020b ; Chen et al,2018a ; Chen et al, 2022 ; Zhang J. et al, 2020 ).…”

Coordination polymerization of nitrogen-rich linkers and dicyanamide anions toward energetic coordination polymers with low sensitivities

“…), such as the reported [Co(N 3 ) 2 (atrz)] n (named CoATRZ, atrz = 4,4′-azo-1,2,4-triazole), 3 [Cu 3 (2-MAT) 2 (N 3 ) 6 ] n (named CMA), 22 {[Co(NH 2 NH 2 ) 5 ](ClO 4 ) 2 } n (named CHP), 23 and (H 2 A)[Ag(ClO 4 ) 3 ] (named PAP-5, H 2 A = piperazine-1,4-diium). 24 Three-component ECPs exhibit enhanced detonation properties. However, the sensitivities of ECPs based on ClO 4 − or N 3 − anions are always very high, which greatly limits their applications.…”