Intramolecular Hydrogen Bonds Assisted Construction of Planar Tricyclic Structures for Insensitive and Highly Thermostable Energetic Materials.

Safety is fundamental for the practical development and application of energetic materials. Three tricyclic energetic compounds, namely, 1,3-di(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (ATDT), 5'-nitro-3-(1H-tetrazol-5-yl)-2'H-[1,3'-bi(1,2,4-triazol)]-5-amine (ATNT), and 1-(3,4-dinitro-1H-pyrazol-5-yl)-3-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (ATDNP), were effectively synthesized through a simple two-step synthetic route. The introduction of intramolecular hydrogen bonds resulted in excellent molecular planarity for the three new compounds. Additionally, they exhibit regular crystal packing, leading to numerous intermolecular hydrogen bonds and π-π interactions. Benefiting from planar tricyclic structural features, ATDT, ATNT, and ATDNP are insensitive (IS > 60 J, FS = 360 N) when exposed to external stimuli. Furthermore, ATNT (Td = 361.1 °C) and ATDNP (Td = 317.0 °C) exhibit high decomposition temperatures and satisfying detonation performance. The intermolecular hydrogen bonding that produced this planar tricyclic molecular structure serves as a model for the creation of innovative multiple heterocycle energetic materials with excellent stability.

Exploring a Fused Triazole-Tetrazine Binary CN Material for a Promising Initiating Substance.

The pursuit of binary carbon-nitrogen (CN) materials with high density and good thermal stability presents a significant challenge due to the inherent trade-off between high-energy storage and low bond dissociation energy. In this study, we designed and synthesized (S)-1,2-bis(3-azido-1H-1,2,4-triazol-1-yl)diazene (BAzTD) and 2,9-diazidobis([1,2,4]-triazolo)[1,5-d:5',1'-f][1,2,3,4]tetrazine (DAzTT) through a straightforward reaction. Remarkably, DAzTT demonstrated a high density of 1.816 g·cm-3 (at 298 K) and a considerable thermal decomposition temperature of 216.86 °C. These properties outperform those of previously reported binary heterocyclic CN compounds and polyazido heterocyclic compounds. The quantum-chemical methods further substantiated the integral role of aromaticity as the driving force behind this difference. Additionally, the initiation capability of DAzTT was evaluated by a notably low minimum primary charge (MPC = 40 mg), surpassing conventional organic primary explosives, such as commercial 2-diazo-4,6-dinitrophenol (DDNP, MPC = 70 mg). The exceptional priming ability highlights the potential as an environmentally friendly replacement for toxic lead azide. DAzTT sets a new standard for binary CN compounds and provides a valuable precursor for high-nitrogen carbon nitride materials.

Backbone Isomerization to Enhance Thermal Stability and Decrease Mechanical Sensitivities of 10 Nitro-Substituted Bipyrazoles.

The development of novel, environmentally friendly, and high-energy oxidizers remains interesting and challenging for replacing halogen-containing ammonium perchloride (AP). The trinitromethyl moiety is one of the most promising substituents for designing high-energy density oxidizers. In this study, a backbone isomerization strategy was utilized to manipulate the properties of 10 nitro group-substituted bipyrazoles containing the largest number of nitro groups among the bis-azole backbones so far. Another advanced high-energy density oxidizer, 3,3',5,5'-tetranitro-1,1'-bis(trinitromethyl)-1H,1'H-4,4'-bipyrazole (3), was designed and synthesized. Compared to the isomer 4,4',5,5'-tetranitro-2,2'-bis(trinitromethyl)-2H,2'H-3,3'-bipyrazole (4) (Td = 125 °C), 3 possesses better thermostability (Td = 156 °C), which is close to that of ammonium dinitramide (ADN) (Td = 159 °C), and it possesses better mechanical sensitivity (impact sensitivity (IS) = 13 J and friction sensitivity (FS) = 240 N) than that of 4 (IS = 9 J and FS = 215 N), thereby demonstrating a promising perspective for practical applications.

N-Functionalization of 5-Aminotetrazoles: Balancing Energetic Performance and Molecular Stability by Introducing ADNP.

5-aminotetrazole is one of the most marked high-nitrogen tetrazole compounds. However, the structural modification of 5-aminotetrazole with nitro groups often leads to dramatically decreased molecular stability, while the N-bridging functionalization does not efficiently improve the density and performance. In this paper, we report on a straightforward approach for improving the density of 5-aminotetrazole by introducing 4-amino-3,5-dinitropyrazole. The following experimental and calculated properties show that nitropyrazole functionalization competes well with energetic performance and mechanic sensitivity. All compounds were thoroughly characterized using IR and NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Two energetic compounds (DMPT-1 and DMPT-2) were further confirmed by implementing single-crystal X-ray diffraction studies. Compound DMPT-1 featured a high crystal density of 1.806 g cm-3, excellent detonation velocity (vD = 8610 m s-1), detonation pressure (P = 30.2 GPa), and impact sensitivity of 30 J.

Intramolecular Assembly of Nitrobiazoles and an Ether Bridge: Toward Energetic Materials with Enhanced Energy and Safety.

Recently, the construction of novel fused-ring frameworks has become one of the most significant innovative approaches to access high-energy and thermostable energetic molecules. In this work, an ether bridge was utilized as a building block to construct energetic fused-ring skeletons for the first time. Two new [5,7,5]-tricyclic N-heterocycle-based backbones, ditriazole-1,3,6-oxadiazepine and pyrazole-triazole-1,3,6-oxadiazepine, were synthesized via a straightforward one-step synthetic route and the energetic performances of their derivatives were further evaluated. Containing an additional oxygen atom, high-density pyrazole-triazole backbone, and high crystal packing coefficient, the asymmetric molecule 2,10,11-trinitro-5H,7H-pyrazolo[1,5-c][1,2,4]triazolo[5,1-e][1,3,6]oxadiazepine (NOB-3) features a high crystal density of 1.825 g cm-3, much superior to those of the symmetrical analogues 2,10-dinitro-5H,7H-bis([1,2,4]triazolo)[1,5-c:5',1'-e][1,3,6]oxadiazepine (NOB-4, d = 1.758 g cm-3) and D (d = 1.634 g cm-3). Meanwhile, the compounds NOB-3 and NOB-4 exhibit better thermal stability than the parent molecule DNBT (Td = 251 °C), and their decomposition temperatures reach up to 303 and 294 °C, respectively. The remarkable overall performance of NOB-3 and NOB-4 strongly suggests them as appropriate candidates for heat-resistant explosives. Our study may give new insights into the close correlation of the structural properties of energetic fused-ring frameworks, and the universality of the asymmetric heterocycles combination strategy for designing advanced high-energy density materials (HEDMs) was emphasized again.

Imidazole-Based Energetic Materials: A Promising Family of N-Heterocyclic Framework.

Imidazole represents a fascinating class of explosophoric units with exciting structures and unique properties. As compared to other nitrogen-rich heterocycles, imidazole demonstrates great potential applications due to economic effectiveness and superior energetic performances. The field of traditional chemistry has been extensively explored for imidazole, and thus established bond-building methods and functionalization strategies promote further development as high-energy density materials (HEDMs). This review addresses the development of energetic imidazole compounds in the past decade, summarizes their physiochemical properties, and is divided into three parts (explosives, propellants, and energetic biocides) according to application requirements. Various synthetic strategies for these energetic molecules are highlighted, including the construction of heterocyclic frameworks and following functionalization. The selected and discussed reactions illustrate the versatility of imidazole in energetic applications as building blocks for the future design of new HEDMs.

Asymmetric assembly of pyrazole and 1,2,3-triazole with a methylene bridge: regioisomerism and energetic properties.

An asymmetric N-bridged strategy was employed to link two different energetic building blocks. The resulting compounds not only exhibit good crystal density and low sensitivity, but also demonstrate the key features of physiochemical properties and regioisomeric structures that enrich the horizon of regiochemistry of energetic compounds.

Enhancement of Energetic Performance through the Construction of Trinitromethyl Substituted ß-Bis(1,2,4-oxadiazole).

Halogen-free substitutions of ammonium perchlorate (AP), which meet the requirements of high density, high performance, and acceptable stability, have been a subject of scientific research for many years. In this work, by regrouping atoms in trinitromethyl substituted bis(1,2,4-oxadiazole), a novel oxidizer, trinitromethyl substituted ß-bis(1,2,4-oxadiazole) (3), was designed and synthesized. It possesses an improved density (ρ = 2.002 g cm-3 at 170 K, ρ = 1.942 g cm-3 at 298 K) and thermal stability (Td = 142.8 °C) in comparison to its regioisomer 5,5'-bis(trinitromethyl)-3,3'-bi(1,2,4-oxadiazole) (E). The properties for 3 were studied by both experimental and theoretical methods. The high positive oxygen balance of +7.3% and high specific impulse of 250 s also make compound 3 a promising candidate for an energetic oxidizer.

Base-mediated regioselective [3+2] annulation of ketenimines and isocyanides: efficient synthesis of 1,4,5-trisubstituted imidazoles.

A novel base-mediated regioselective [3+2] annulation of active methylene isocyanides with ketenimines has been developed. In the presence of t-BuOK, a wide range of ketenimines readily react with active methylene isocyanides in DMF at 40 °C to afford 1,4,5-trisubstituted imidazoles efficiently.

Silver-Catalyzed Chemoselective [4+2] Annulation of Two Isocyanides: A General Route to Pyridone-Fused Carbo- and Heterocycles.

A silver-catalyzed chemoselective [4+2] annulation of aryl and heteroaryl isocyanides with α-substituted isocyanoacetamides was developed for the facile and efficient synthesis of 2-aminoquinolones, naphthyridines, and phenanthrolines. A mechanism for this multistep domino reaction is proposed on the basis of a 13 C-labeling experiment, according to which an unprecedented chemoselective heterodimerization of two different isocyanides generates an α-amidoketenimine intermediate, which undergoes 1,3-amino migration to form an α-imidoylketene, followed by 6 π electrocyclization.