Combined Computational and Experimental Study on Designing Balanced Tetrazole-Based Energetic Materials

Abstract

Herein, we present an integrated computational and experimental strategy for the rational design of tetrazole-based energetic materials that overcome the classical trade-off between high energy density and low sensitivity. Theoretical screening identified tetrazole-based molecular skeleton as promising energetic candidates, exhibiting predicted densities up to 2.02 g/cm³ and enhanced stability, which was attributed to widened HOMO-LUMO gaps (6.56-8.68 eV) and the stabilizing influence of introduced energetic tetrazole-skeleton. Further analysis of model systems (molecule I-09 and II) confirmed strong aromaticity and stable dimer formation governed by van der Waals and electrostatic interactions. Guided by these computational insights, derivatives A and B were synthesized using I-09 and II as structural templates. The derivative A exhibited a high thermal decomposition onset (T_d 217.55 °C) and relatively lower sensitivity. Single-crystal X-ray diffraction analysis of derivative A revealed a well-defined “face-to-face” π-π stacking arrangement, arising from weak intermolecular interactions. Collectively, this study demonstrated that precise control over both the electronic structure and the solid-state arrangement enabled an effective balance between detonation properties and sensitivity. The consistency between theoretical prediction and experimental validation established a reliable design strategy for the development of advanced and insensitive high-energy materials.