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Abstract
New energetic materials, [Ca(MCZ)3(H2O)2](ClO4)2 and {[Ba2(MCZ)4(H2O)2(μ1-ClO4)2(μ2-ClO4)2]0.5}n, are synthesized and tried as alternatives to common primary explosives. Both the crystal structures were determined by single-crystal X-ray diffraction. The crystal of [Ca(MCZ)3(H2O)2](ClO4)2 belongs to the monoclinic, P21/c space group, a = 14.168(3) Å, b = 8.5938(18) Å, c = 18.889(4) Å, β = 111.234(2)°, V = 2143.8(8) Å3, ρ = 1.6893 g cm−3, and {[Ba2(MCZ)4(H2O)2(μ1-ClO4)2(μ2-ClO4)2]0.5}n belongs to the triclinic, P-1 space group, a = 7.166(2) Å, b = 10.461(2) Å, c = 11.738(4) Å, α = 110.563(5)°, β = 93.799(2)°, γ = 96.864(3)°, V = 812.4(4) Å3, ρ = 2.185 g cm−3. Their thermal stabilities were investigated by differential scanning calorimetry (DSC), and exothermic peak temperatures with a heating rate of 10 °C min−1 are 249.7 and 181.7 °C, respectively. Non-isothermal reaction kinetics parameters were calculated via both Kissinger’s method and Ozawa-Doyle’s method to work out EK = 124.6 kJ mol−1, lgAK = 10.38, EO = 126.7 kJ mol−1 for the calcium complex and EK = 100.3 kJ mol−1, lgAK = 9.50, EO = 102.6 kJ mol−1 for the barium complex. Additionally, the critical temperatures of thermal explosion, ΔS≠, ΔH≠, and ΔG≠ were calculated as −231.2 J K−1 mol−1, 120.417 kJ mol−1, 236.728 kJ mol−1 for the calcium complex and −230.6 J K−1 mol−1, 96.723 kJ mol−1, 195.938 kJ mol−1 for the barium complex. As for their explosive nature, sensitivities toward impact and friction were tested. Both [Ca(MCZ)3(H2O)2](ClO4)2 and {[Ba2(MCZ)4(H2O)2(μ1-ClO4)2(μ2-ClO4)2]0.5}n are insensitive to friction (>360 N); their impact sensitivities are acceptable (20 and 13 J). Both compounds are energetic complexes.
Disclosure statement
No potential conflict of interest was reported by the authors.