Asymmetrically substituted 5,5′-bistriazoles – nitrogen-rich materials with various energetic functionalities

Abstract

In this contribution the synthesis and full structural and spectroscopic characterization of three asymmetrically substituted bis-1,2,4-triazoles, along with different energetic moieties like amino, nitro, nitrimino and azido moieties, is presented. Additionally, selected nitrogen-rich ionic derivatives have been prepared and characterized. This comparative study on the influence of these energetic moieties on structural and energetic properties constitutes a complete characterization including IR, Raman and multinuclear NMR spectroscopy. Single crystal X-ray crystallographic measurements were performed and provide insight into structural characteristics as well as inter-and intramolecular interactions. The standard enthalpies of formation were calculated for all compounds at the CBS-4M level of theory, revealing highly positive heats of formation for all compounds. The detonation parameters were calculated using the EXPLO5 program and compared to the common secondary explosive RDX as well as recently published symmetric bistriazoles. As expected, the measured sensitivities to mechanical stimuli and decomposition temperatures strongly depend on the energetic moiety of the triazole ring. All compounds were characterized in terms of sensitivities (impact, friction, electrostatic) and thermal stabilities, the ionic derivatives were found to be thermally stable, insensitive compounds.

A 1D cadmium complex with 3,4-diamino-1,2,4-triazole as ligand: synthesis, molecular structure, characterization, and theoretical studies

“…Recently, considerable attention has been paid to the study of nitrogen-rich azole compounds as potential energetic materials. Azole-based heterocyclic compounds contain several advantages, such as smokeless combustion, good thermal stability and positive heat of formation [5][6][7][8], which could be due to the existence of a large number of N-N and C-N bonds [9][10][11][12][13][14][15][16].…”

Construction of Coplanar Bicyclic Backbones for 1,2,4‐Triazole‐1,2,4‐Oxadiazole‐Derived Energetic Materials

“…However, compounds B and C exhibit noticeably different properties when different heterocycles are introduced into the 1,2,4‐triazole ring but contain the same energy groups. Compared to B ( d =1.70 g cm −3 , P =26.1 GPa, D =7925 m s −1 ), [7] with the introduction of furazan to provide compound C , [5a] the thermal stability, mechanical sensitivity, and density improved remarkably ( T d =163 °C, d =1.85 g cm −3 , IS=20 J) and the detonation parameters ( P =36.0 GPa, D =9025 m s −1 ) are still comparable to A . Therefore, energetic backbones with desirable comprehensive properties can be constructed by linking 1,2,4‐triazole with other N‐heterocycles.…”

Exploring Application of 1,2,4‐Triazole Energetic Salts: Gas Generating Agent, Propellant and Explosive Compositions

“…Since the 18th century, the industrial revolution has gradually entered a stage of rapid development with the advent of safe nitroglycerin. The employment of energetic materials (EMs) opens a new era in the development of human society [1–3]. “Good detonation performance, non‐toxicity on the environment, safety during transportation, stability during storage…” are essential properties to attain applied standards for modern advanced energetic materials [4, 5].…”