Molecular design and theoretical assessment of high-energy tetrazole-nitropyrazole compounds: balancing performance...

Inspired by tetracyclic nitropyrazole-based stable and potential energetic materials, we designed two new C-C and C-N-linked tetrazole-pyrazole-based energetic molecules, with acceptable detonation performance and moderate sensitivity. The heat of formation and performance parameters were analyzed by density functional theory, and the calculations demonstrate that both compounds have a high positive heat of formation (> 930 kJ/mol). The designed compounds, A1 (density: 1.79 g/cm³, detonation velocity: 7.95 km/s, pressure: 25.30 GPa, impact sensitivity: 35 J) and A2 (density: 1.87 g/cm³, detonation velocity: 8.83 km/s, pressure: 33.31 GPa, impact sensitivity: 21 J), exhibit moderate to high detonation performance and low sensitivity to impact stimuli. Further, the analysis of bond strength and Mayer bond order of the C-NO₂ bond and charge on -NO₂ groups suggests the stability of the C-NO₂ bond in designed compounds in comparison with reported tetracyclic energetic compounds. These findings demonstrate that the combination of bistetrazole with nitropyrazole and dinitropyrazole rings holds high potential for developing new high-performing and less sensitive energetic materials.

The optimization and energy calculations of designed tetracyclic compounds were carried out at the B3LYP/6-311G(d,p) level of theory, utilizing the Gaussian 09 software package. The molecular surface properties were analysed using Multiwfn. The EXPLO5 (V7.01.01) thermochemical code was used to predict the detonation properties.