Synthesis and characterization of the layered insensitive pentazolate salts based on two triazolium isomers

Abstract

The all-nitrogen cyclo-pentazolate (c-N5ˉ) anion has attracted interest because of its promising application in high-energy materials. Now, nonmetallic pentazolate salts were prepared by assembling cyclo-N5ˉ and cations but it was shown to be challenging to balance excellent detonation performance and good stability, which results in restrictions for practical applications. However, we find the layer-by-layer crystal stacking structure can enhance the sensitivity of pentazolate salts. Herein, we designed and synthesized two targeted cyclo-pentazolate salts with layered stacking mode in their crystal structures based on two isomeric cations: 3,4,5-triamino-1,2,4-triazolium and 3-hydrazino-4-amino-1,2,4-triazolium. The results demonstrate that the aromaticity of triazole and pentazole rings arouse the π−π interaction force, promoting the formation of a layer-by-layer crystal stacking structure. Two compounds show very low sensitivity characteristics (FS>40 and IS>360) and good detonation properties (detonation velocity: 3, Dv= 8796m⋅s−1; 4, Dv=8574m⋅s−1. detonation pressure: 3, P = 26.6 GPa; 4, P = 25.1 GPa). Computational analysis based on noncovalent interaction index, localized orbital locator-π and electron density difference provide a better understanding about the effects of layer-by-layer stacking structure on the stabilities. These findings contribute to preparation of both high-energy and low sensitivity pentazolate salts.