A Family of Methylene‐Bridged Fully Functionalized Polynitroarenes and Tetrazole‐Based Energetic Materials

Herein, to fine‐tune the energetic properties of 2,4,6‐trinitrobenzene‐1,3‐diamine/diol, these are combined with tetrazole via a methylene bridge. This strategy unlocks the tunability of polynitroarenes performances via salt formation, which is restricted in directly CN connected polynitroarenes and azole derivatives. The amino/hydroxy functionalities between the nitro groups on the benzene ring provide extensive inter‐ and intramolecular hydrogen bonding interactions, contributing to improved stability, whereas the tetrazole ring increases the nitrogen percentage and energetic performance. Due to the presence of one and three labile protons in the amino derivative (compounds 4 ) and hydroxy derivative (compounds 5 ), respectively, a series of mono‐ and tricationic salts are prepared to further fine‐tune the overall performances. Among all the synthesized compounds, the tricationic energetic salt 10 (D v = 8135 m s −1 , IS > 40 J) exhibits energetic performance comparable to TATB and is insensitive. All the compounds are characterized through infrared spectroscopy, Nuclear Magnetic Resonance (NMR) spectroscopy, differential scanning calorimetry, elemental analysis, and high‐resolution mass spectra studies. The relationship between structure and properties is further explored using Hirshfeld surface, noncovalent interaction, Localized Orbital Locator (LOL)‐π, and electrostatic potential analysis.