Syntheses and Promising Properties of Dense Energetic 5,5′‐Dinitramino‐3,3′‐azo‐1,2,4‐oxadiazole and Its Salts

Abstract

A planar energetic molecule with high density, 5,5′-dinitramino-3,3′-azo-1,2,4-oxadiazole (4), was obtained by the nitration of 5,5′-diamino-3,3′-azo-1,2,4-oxadiazole using 100% nitric acid. In addition, selected nitrogen-rich salts were prepared. Among them, the neutral compound 4 and its hydroxylammonium salt, 6, were further confirmed by single-crystal X-ray diffraction. Physicochemical and energetic properties including density, thermal stability and sensitivity were investigated. The energetic performance from the calculated heats of formation and experimental densities indicates that many of them have potential applications as energetic materials.

Molecular perovskite high-energetic materials

“…Loading more nitro groups and higher structural tension into a single molecule does improve explosive performance, but usually leads to complicated and not cost-effective synthetic procedures. By a trade-off of detonation performance and cost, HMX is regarded as the best military high-energetic explosives nowadays [7], although it is neither the most powerful one nor the cheapest one.Parallel to the intensive studies on molecule engineering on the backbone of nitrogen-rich organic energetic molecules [8,9], the exploration of advanced energetic materials extends to the crystal engineering on their energetic co-crystals [10-13], energetic salts [14][15][16][17][18][19][20], as well as coordination polymers or metal-organic frameworks [21][22][23][24][25][26][27]. The essential strategy is to control the intermolecular packing/linkage of the energetic organic fuel and oxidizer components in crystals by non-covalent interactions to modify/enhance the explosive performance and/or to reduce the sensitivity to a practicable level.…”

A New Energetic Salt Semicarbazide 5-Dinitromethyltetrazolate: A Promising Explosive Alternative

“…A new energetic salt, semicarbazide 5-dinitromethyltetrazolate (SCZ·DNMZ), was designed and synthesized by using semicarbazide and 5-dinitromethyltetrazolate (DNMZ) as raw materials. The compound was characterized by elemental analysis, Fourier Transform infrared spectroscopy 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 (FT-IR) spectroscopy, 1 H, 13 C and 15 N nmR and mass spectrometry. The structure is also settled through single-crystal X-ray diffraction and the results show that the salt belongs to the monoclinic system with space group P2 1 /c and a relatively high density of 1.867 g cm À3 .…”

“…The FT-IR spectra were recorded with a Bruker Equinox 55 infrared spectrometer in the range of 4000-400 cm À1 by using KBr pellets with a resolution of 4 cm À1 . 1 H, 13 C, and 15 N nmR spectra were obtained with a JEOLJNM-ECA400 at 400 MHz. Differential scanning calorimeter (DSC) and thermogravimetric analysis (TG) measurements were carried out with a Pyris-1 differential scanning calorimeter and a Pyris-1 thermogravimetric analyzer (Per-kin-Elmer, USA) at a heating rate of 5 K min À1 in a dry nitrogen atmosphere with a flowing rate of 20 mL min À1 .…”

“…Nitrogen-rich heterocyclic compounds, including furazan, tetrazine, triazole, and tetrazole, always show prominent properties such as high density, low sensitivity, and strong environmental acceptability [7][8][9][10][11][12]. Various researches have favored the development of such heterocyclic compounds and derivatives [13][14][15], in which the tetrazole compound is a unique category. One of the outstanding advantages for the tetrazole is the high nitrogen content, which ensures a high heat of formation, eventually leading to a large amount of energy released when detonation process occurs [16][17][18].…”

Green Energetic Nitrogen‐Rich Salts of 1,1′‐Dinitramino‐5,5′‐bistetrazolate

“…[11] Compared with alkali metals as cations, nitrogen-rich cations are more popular because of ap otentialh ydrogenbond network and ah ighp ositive heat of formation. [1,[13][14][15][16][17][18][19] Among the nitrogen-rich heterocycles, tetrazoles occupy an intermediate positiono nt he "stability versus performance" continuum, [20] therebyo ffering intriguing structural backbones for the designa nd construction of new high-energy density materials (HEDMs). Versatile energetic ionic salts have been well documented and potentially used in explosives, gas generators, smoke-free pyrotechnic fuels, solid fuels in micro-propulsion system, effective precursors for carbon nitride nanomaterials, and pharmaceutical fields.…”