Correlation between Structure and Energetic Properties of Three Nitroaromatic Compounds: Bis(2,4-dinitrophenyl) Ether, Bis(2,4,6-trinitrophenyl) Ether, and Bis(2,4,6-trinitrophenyl) Thioether

Abstract

Decades after the initial discovery of bis (2,4,6trinitrophenyl) ether derivatives, the first single-crystal X-ray structures for three members of this compound class can finally be shown and the analytical data could be completed. This group of molecules is an interesting example that illustrates why older predictive models for the sensitivity values of energetic materials like bond dissociation enthalpy and electrostatic potential sometimes give results that deviate significantly from the experimentally determined values. By applying newer models like Hirshfeld surface analysis and fingerprint plot analysis that utilize the crystal structure of an energetic material, the experimentally found trend of sensitivities could be understood and the older models could be brought into a proper perspective. In the future, the prediction of structure−property relationships for energetic molecules starting from a crystal structure can be achieved and should be pursued.

Heat‐Resistant Energetic Materials Deriving from Benzopyridotetraazapentalene: Halogen Bonding Effects on the Outcome of Crystal Structure, Thermal Stability and Sensitivity

“…Here, Kissinger and Ozawa‐Doyle's methods are conducted based on the first exothermic peak temperatures ( T p ) measured at different heating rates of 5, 10, 15, 20 °C min −1 . As shown in Figure 4(d)‐4(f), under the heating rate of 5 °C min −1 , the decomposition of compound 6‐a commenced at 334.13 °C, and reached the peak at 347.91 °C incredibly, which is superior to most of heat‐resistant explosives such as TNT ( T d : 295 °C) [9], HNS ( T d : 318 °C) [6], bis(2,4,6‐trinitrophenyl) ether (BTNPE) ( T d : 256 °C) [1] and bis(2,4,6‐trinitrophenyl) (BTNPTE) ( T d : 310 °C) [1], but slightly lower than that of BPTAP ( T d : 366 °C). Compound 6‐b started to decompose at 324.5 °C, and arrived at 330.53 °C as its peak, which also surpasses those of TNT and HNS.…”

“…Among them, heat‐resistant energetic material (HREM) has shown its broad applications in petroleum and natural gas exploration, aerospace vehicle as well as solid rocket formulations. Since the discovery of 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB) and hexanitrosilbene (HNS), heat‐resistant aromatic energetic compounds have attracted much attention for the development and production of the‐next‐generation energetic materials in applications [1]. However, the insufficiency of nitrogen atoms in the above‐mentioned materials lead to the low energy output for energetic devices [2].…”

“…For energy materials, halogen is applied in the design and preparation of highly efficient perovskite solar cells and materials (CH 3 NH 3 PbX 3 , X=I, Cl) [18, 19], flexible and elastic organic crystal [20–22], hypergolic ionic liquid, etc. For energetic materials, halogen is significant in the structural establishment of energetic biocidal agents (iodine based polynitro compounds), solid rocket propellants (ammonium perchlorate, etc) [23] as well as thermally stable energetic materials [1,3,5‐trichloro‐2,4,6‐trinitrobenzene (TCTNB), 1,3,5‐triiodo‐2,4,6‐trinitrobenzene (TITNB), 1,3,5‐tribromo‐2,4,6‐trinitrobenzene (TBTNB), etc] [1], and so on. In recent years, chlorine has been also found in building a series of molecular‐perovskite energetic materials [24–26] and host‐guest explosives with the incorporation of perchlorate ions [27–31].…”

A Study of 3,5‐Dinitro‐1‐(2,4,6‐trinitrophenyl)‐1H‐pyrazol‐4‐amine (PicADNP) as a New High Energy Density Booster Explosive

“…The ortho nitro groups of the benzene ring show torsion angles of 38.9°(C2-nitro) and 18.8°(C6-nitro), which is a very common observation for trinitrobenzene derivatives. [17,18] This behavior is usually explained by a combination of steric effects and electronic repulsion between the substituent at the 1-position and the ortho nitro groups. [17,18] For PicADNP, the discussed torsion of the substituents facilitates a minimization of the repulsion between neighboring nitro groups and reduces the repulsion between the pyrazole ring and the C2-nitro group.…”

Analysis of the Explosive Properties of Tetrasulfur Tetranitride, S4N4

“…However, it was only very recently that its amorphization (a prerequisite for facile reaction and ignition) when brought into contact with freshly activated carbon was discovered independently [2,3] . Apart from its pivotal role in black powder and similarly composed pyrotechnics, [4,5] elemental sulfur [6–8] and its compounds [9,10] scarcely find use in todays energetic materials and also have gained very little research interest. Nitrogen on the other hand is so ubiquitous in energetic materials, it does not require an introduction.…”