Synthesis and properties of novel nitrogen- and oxygen-enriched dicationic 3,4-diaminotriazolium salts as attractive energetic materials

The incorporation of both fuel and oxidizer properties into a single molecule to effectively improve the oxygen balance of energetic compounds has become one of the most acceptable strategies for the design of modern high-energy-density materials (HEDMs). To identify more powerful and less sensitive HEDMs with favorable oxygen balance, novel nitrogen- and oxygen-enriched dicationic 3,4-diaminotriazolium salts were prepared via the quaternization of 3,4-diamino-triazole with 4,4′-bis(nitramino)azofurazan and 4,4′-bis(nitramino)azoxyfurazan, and then fully characterized. These compounds exhibited favorable thermal stabilities with decomposition temperatures up to 216°C, high densities over 1.82 g·cm⁻³ as well as acceptable sensitivities. In addition, the two-dimensional fingerprint spectra based on Hirshfeld surface analysis were adopted to illustrate structure–property relationships. Based on the combination of experimentally determined densities and heats of formation calculated with Gaussian 03, the energetic properties were determined using the EXPLO5 v6.02 program. The newly synthesized ionic salts displayed excellent detonation properties (V_d, 9115-9220 m·s⁻¹; P, 33.9-35.4 GPa), comparable to those of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), thus highlighting their potential in energetic material applications.