Energetic Multifunctionalized Nitraminopyrazoles and Their Ionic Derivatives: Ternary Hydrogen-Bond Induced High Energy Density Materials

Diverse
functionalization was introduced into the pyrazole framework
giving rise to a new family of ternary hydrogen-bond induced high
energy density materials. By incorporating extended cationic interactions,
nitramine-based ionic derivatives exhibit good energetic performance
and enhanced molecular stability. Performance parameters including
heats of formation and detonation properties were calculated by using Gaussian 03 and EXPLO5 v6.01 programs,
respectively. It is noteworthy to find that 5-nitramino-3,4-dinitropyrazole, 4, has a remarkable measured density of 1.97 g cm–3 at 298 K, which is consistent with its crystal density (2.032 g
cm–3, 150 K), and ranks highest among azole-based
CHNO compounds. Energetic evaluation indicates that, in addition to
the molecular compound 4, some ionic derivatives, 9, 11, 12, 17, 19, and 22, also have high densities (1.83–1.97
g cm–3), excellent detonation pressures and velocities
(P, 35.6–41.6 GPa; vD, 8880–9430 m s–1), as well as acceptable
impact and friction sensitivities (IS, 4–30 J; FS, 40–240
N). These attractive features highlight the application potential
of nitramino hydrogen-bonded interactions in the design of advanced
energetic materials.

将多样化官能化策略引入吡唑骨架，由此构建出一类新型三元氢键诱导高能量密度材料家族。通过引入扩展型阳离子相互作用，硝胺基离子型衍生物展现出优异的含能性能与提升的分子稳定性。研究分别采用Gaussian 03与EXPLO5 v6.01程序，计算了生成焓与爆轰性能等关键性能参数。值得关注的是，化合物4——5-硝氨基-3,4-二硝基吡唑——在298 K下的实测密度达1.97 g·cm⁻³，与其在150 K下的晶体密度（2.032 g·cm⁻³）相符，且在唑类CHNO含能化合物中位列第一。含能性能评估结果显示，除分子型化合物4外，部分离子型衍生物（编号9、11、12、17、19与22）同样具备较高密度（1.83~1.97 g·cm⁻³）、优异的爆压与爆速（P：35.6~41.6 GPa；v_D：8880~9430 m·s⁻¹），以及可接受的撞击感度与摩擦感度（IS：4~30 J；FS：40~240 N）。上述优异特性凸显了硝氨基氢键相互作用在先进含能材料设计中的应用潜力。