Abstract
Nitramine-based energetic materials must balance high detonation performance with acceptablethermal and mechanical stability, a challenge that is particularly pronounced for nitrogen-richheterocycles bearing labile N-NO2 linkages. Herein, a controlled and selective stepwisenitramination strategy affords a neutral bisnitramino triazole, N,N′-(3-nitro-1H-1,2,4-triazole-1,5-diyl)dinitramide (BNT), together with its corresponding ionic derivatives. BNT is a dense energeticcompound (ρ = 1.941 g cm-3; Dv = 9507 m s-1) and exhibits pronounced triazole nitramineconjugation, as evidenced by real-space LOL-π analysis. Electronic-structure analysis revealssubstantial nitro-group delocalization (Q̅nitro = -0.226) and identifies a weak N-NO2 linkage (BDE= 85.2 kJ mol-1) that governs the intrinsic sensitivity of the neutral framework. Conversion of BNTinto the corresponding diammonium (BNTDA) and dihydrazinium (BNTDHD) ionic derivativesstabilizes the energetic lattice through extended hydrogen-bonding interactions, markedly reducingimpact and friction sensitivities while retaining high detonation performance. Notably, BNTDHDachieves an ultrahigh detonation velocity of 10,018 m s-1 together with enhanced thermal stabilityand moderated mechanical sensitivity. Comparative analysis of the C-NHNO2 and C-NO2 systemsdemonstrates that incorporation of C-NHNO2 promotes conjugative delocalization and electronicredistribution within the triazole framework, leading to stabilization of the dinitramine structureand modulation of N-NO2 bond strength. These results establish electronic regulation of N-NO₂bonding as a viable design strategy for developing dense, high-performance energetic materialswith improved operational safety.