Energetic Salts of Sensitive N,N′-(3,5-Dinitropyrazine-2,6-diyl)dinitramide Stabilized through Three-Dimensional Intermolecular Interactions

Abstract

N-nitration of 2,6-diamino-3,5-dinitropyrazine (ANPZ) leads to a sensitive energetic compound N,N′-(3,5dinitropyrazine-2,6-diyl)dinitramide. This nitro(nitroamino) compound was stabilized by synthesizing energetic salts, dipotassium (3,5-dinitropyrazine-2,6-diyl)bis(nitroamide) (3) and diammonium (3,5-dinitropyrazine-2,6-diyl)bis(nitroamide) (4). Compounds 3 and 4 are fully characterized by single-crystal X-ray diffraction. Compound 3 exhibits a three-dimensional energetic metal−organic framework (3D EMOF) structure and an outstanding overall performance by combining high experimental density (2.10 g cm −3 ), good thermal stability (T d(onset) = 220 °C), and good calculated performance of detonation (D = 8300 m s −1 , P = 29.9 GPa). Compound 4 has acceptable thermal stability (155 °C), moderate experimental density (1.73 g cm −3 ), and good calculated performance of detonation (D = 8624 m s −1 , P = 30.8 GPa). The sensitivities of compounds 3 and 4 toward impact and friction were determined following standard methods (BAM). The energetic character of compounds 3 and 4 was determined using red-hot needle and heated plate tests. The results highlight a 3D EMOF (3) based on a six-membered heterocycle as a potential energetic material.

Solvent Free Potassium 3,5‐dinitro‐6‐oxo‐1,6‐dihydropyrazin‐2‐olate 3D EMOF as Thermally Stable Energetic Material

“…The DSC curve shows a small endothermic peak at 193 °C before decomposition. As can be seen in Figure S6, it shows a very sharp onset decomposition temperature at 291 °C with 5 °C min À 1 heating rate, which is better than the previously reported potassium EMOFs K 2 DNPDP [28] (220 °C), K 2 DNAF [24] (288 °C) and close to K 2 DNADFP [18] (292 °C), K 2 NPA [27] (315 °C), and also higher or close to the present commonly used heat-resistant explosive HMX (279 °C) and HNS (318 °C). The TGA curve exhibits two distinct weight loss peaks under a heating rate of 5 °C min À 1 .…”

“…Recently, Shreeve and coworkers reported the potassium EMOF based on six‐membered N,N′‐(3,5‐dinitropyrazine‐2,6‐diyl)dinitramide, which possesses high sensitivity and lower thermal decomposition temperature owing to the presence of two nitro and nitramino groups in the ligand (Scheme 1). [28] Among six‐membered heterocycles, pyrimidines and pyrazines exhibit great potential in the field of energetic materials due to their versatile, modifiable positions for incorporating different explosophoric groups. Numerous studies have shown that these compounds possess excellent thermal stability and maintain low sensitivity to external factors [21,29,30] .…”

Amine and nitramine functionalization of imidazole‐triazine and triazole‐triazine skeletons: Exploring for potential multipurpose energetic materials

“…Heterocyclic backbones, such as the five-and sixmembered rings (pyrazole, imidazole, triazole, tetrazole, oxadiazole, pyrazine, triazine, pyrimidine, pyridazine, and tetrazine), are commonly regarded as the primary building blocks of modern high energy density materials (HEDMs) [11,[14][15][16][17][18]. The incorporation of various explosophoric groups such as nitro (-NO 2 ), nitramine (-NHNO 2 ), azide (-N 3 ), etc., on a particular heterocyclic framework is a widely used and effective strategy to boost the detonation performance of the compounds [19][20][21][22].…”

Pushing the Limit of Oxygen Balance on a Benzofuroxan Framework: K2DNDP as an Extremely Dense and Thermally Stable Material as a Substitute for Lead Azide

“…Due to the coordination ability of the potassium ions, energetic coordination compounds (ECCs) formed by potassium−oxygen cooperation have attracted special attention owing to their unique structures, good energetic properties, and acceptable densities (∼2.0 g cm −3 ). 22 density (ρ < 2.0 g cm −3 ), and inferior oxygen balance (negative).…”

“…Notable examples include DTAT-K, K 2 DNABT, potassium 4,5-bis­(dinitromethyl)­furoxanate, and K 2 BDFOF (Figure b). Due to the coordination ability of the potassium ions, energetic coordination compounds (ECCs) formed by potassium–oxygen cooperation have attracted special attention owing to their unique structures, good energetic properties, and acceptable densities (∼2.0 g cm –3 ) . However, in comparison with LA ( T dec = 315 °C; d = 4.80 g/cm 3 ), most of the potassium-based initiators have poor thermal stability ( T dec < 200 °C), lower density (ρ < 2.0 g cm –3 ), and inferior oxygen balance (negative).…”