Zwitterionic Energetic Materials: Synthesis, Structural Diversity and Energetic Properties

Chemistry - An Asian Journal, Год журнала: 2024, Номер 19(17)

Опубликована: Июнь 10, 2024

Abstract Zwitterionic compounds are an emergent class of energetic materials and have gained synthetic interest many in the recent years. Due to their better packing efficiencies strong inter/intramolecular electrostatic interactions, they often ensue superior properties than salt analogues. A systematic review from perspective design, synthesis, physicochemical evaluation zwitterionic is presented. Depending on parent ring(s) used for synthesis type moieties bearing positive negative charges, different classes materials, such as primary explosives, secondary heat resistant oxidizers, etc., may result. The some also compared with analogous salts. This will encourage readers explore possibility designing new materials.

Язык: Английский

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Single Step Synthesis of gem-Dinitro Methyl-1,2,4-triazole and Its Hydroxylamine Salt: An Alternative to the FOX-7 and Other Benchmark Explosives

Organic Letters, Год журнала: 2024, Номер 26(22), С. 4788 - 4792

Опубликована: Май 29, 2024

gem-Dinitro methyl based high-energy-density material 5-(dinitromethylene)-4,5-dihydro-1H-1,2,4-triazole (2) and its hydroxylamine salt (4) were synthesized for the first time in a single step characterized. Further, structure of 2 was confirmed by single-crystal X-ray diffraction (SCXRD) studies. Interestengly, both compounds show excellent density (> 1.83 g cm-3), detonation velocity 8700 m s–1), pressure 30 GPa) are insensitive toward mechanical stimuli such as impact friction sensitivity. Considering their synthetic fesibility balanced energetic performance, 4 future prospects potential next-generation materials replacenent many presently used benchmark high energy RDX, FOX-7 highly H-FOX.

Язык: Английский

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Mixed-Metallic Energetic Metal–Organic Framework: New Structure Motif for Potential Heat-Resistant Energetic Materials

Crystal Growth & Design, Год журнала: 2024, Номер 24(5), С. 2142 - 2148

Опубликована: Фев. 20, 2024

The incessant pursuit of heat-resistant explosives with balanced energetic performance and safety is indispensable in civil military sectors, particularly when employed harsh environments. Herein, a new nanostructured highly metal–organic framework (E-MOF), based on nickel(II) sodium(I) mixed-metal has been constructed using an poly tetrazole molecule by the hydrothermal approach. Na/Ni-MOF was thoroughly characterized infrared radiation (IR), thermogravimetric analysis differential scanning calorimetry, electron microscopy, powder X-ray diffraction analyses. Further, crystal structure authenticated single analysis, their packing features were well explored, revealing wave-like 3D having density 1.985 g cm–3. This mixed-metallic E-MOF demonstrated good enthalpy combustion (−7.91 kJ·g–1), velocity detonation (VOD = 7410 m s–1) exceeding that trinitrotoluene (TNT, 6820 m/s) Hexanitrostilbene (HNS, 7164 m/s), excellent insensitivity [impact sensitivity (IS) > 40 J friction (FS) 360 N]. Additionally, it exhibits outstanding thermal stability (Td 387 °C). These fine-tuned properties are superior to those continuously used benchmark HNS 2,4,6-triamino-1,3,5-trinitrobenzene, suggesting newly reported tetrazole-based beneficial for improved physical performance. results given present work highlighted advantages as potential explosive future applications.

Язык: Английский

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Constructing Nitrogen-Rich Fused [5,6,5]-Tricyclic Frameworks Through Rearrangement: Heat-Resistant Zwitterionic Salt Energetic Materials

Organic Letters, Год журнала: 2024, Номер 26(47), С. 10085 - 10089

Опубликована: Ноя. 8, 2024

This study synthesized nitrogen-rich [5,6,5] fused compounds through a novel rearrangement reaction. Owing to its unique zwitterionic salt structure, product 4-1 exhibits high thermal stability (Td > 250 °C), low sensitivity (IS 40 J, FS 360 N), and acceptable detonation velocities pressures (νD = 8520 m s–1 P 32.53 GPa, respectively), which are better than those of TNT TATB. These indicate the potential salts as thermally stable energetic materials provide new synthesis strategies for constructing polycyclic heterocycles rearrangement.

Язык: Английский

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Intramolecular Cyclization and Energetic Group Modifications for Thermally Stable and Low-Sensitivity Monocyclic Dinitromethyl Zwitterionic Pyrazoles

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

Zwitterionic energetic materials offer a unique combination of high performance and stability, yet their synthesis stability enhancement remain key challenges. In this study, we report the highly stable (dinitromethyl-functionalized zwitterionic compound, 1-(amino(iminio)methyl)-4,5-dihydro-1H-pyrazol-5-yl)dinitromethanide (4), with thermal decomposition temperature 215 °C, surpassing that most previously reported monocyclic zwitterions (Td < 150 °C). This compound was synthesized via intramolecular cyclization trinitromethyl-functionalized hydrazone precursor. Further chemical modifications, including nitration fluorination, enabled zwitterion-to-zwitterion transformations, resulting in formation nitramines 10 12. Additionally, perchlorate salt (8) 4 synthesized, along ammonium (13), guanidinium (14), potassium (15) salts derived from 10, all retaining properties. Physicochemical evaluations reveal zwitterion 12 exhibits excellent = 181 °C) an optimal balance between energy output (detonation velocity: 8329 m s-1, detonation pressure: 29.4 GPa) reduced sensitivity (impact sensitivity: 35 J, friction 320 N). Notably, 15 demonstrates superior 233 °C), exceeding RDX. These results expand design framework for contribute to development high-energy, low-sensitivity materials.

Язык: Английский

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New Zwitterionic Compounds Based on 1-(tetrazol-5-yl)-1,2,4-triazole: High-Energy, Low-Sensitivity Energetic Materials

Journal of Molecular Structure, Год журнала: 2025, Номер unknown, С. 141579 - 141579

Опубликована: Янв. 1, 2025

Язык: Английский

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Exploring Green Pyrotechnic Formulations and Primary Explosives with 1,3,4‐Oxadiazole‐Based Micro and Submicron Energetic Coordination Polymers

Small, Год журнала: 2025, Номер unknown

Опубликована: Янв. 29, 2025

Abstract Alkali and alkaline‐earth metal incorporated 5,5′‐dinitramino‐3,3′‐azo‐1,3,4‐oxadiazole (H 2 DNAO) based Energetic Coordination Polymers (ECPs), namely dipotassium 5,5′‐dinitramino‐3,3′‐azo‐1,3,4‐oxadiazole(K DNAO), dicesium 5,5′‐dinitramino‐3,3′‐azo‐1,3,4‐oxadiazole(Cs barium 5,5′‐dinitramino‐3,3′‐azo‐1,3,4‐oxadiazole(BaDNAO) are synthesized for the first time. Synthesized ECPs thoroughly characterized using infrared spectroscopy (IR), elemental analysis (EA), thermogravimetric differential scanning calorimetry (TGA‐DSC), field emission electron microscopy (FE‐SEM), dynamic light scattering (DLS), UV–vis spectroscopy. All also confirmed by single‐crystal X‐ray diffraction technique (SC‐XRD). The micro‐ECPs exhibit excellent densities (1.98–2.80 g cm −3 ), insensitivities (IS: 25‐40 J; FS: 240‐360 N), good thermal stabilities ( T d : 182–212 °C). K DNAO Cs show detonation performance (VOD:7460‐7893 m s −1 ; DP: 27.5‐30.6 GPa), respectively. To further investigate sub‐micron‐energetics, three sub‐micron prepared from their micro counterparts ultrasonication method, demonstrating significant improvement in stability 194–221 °C) but highly sensitivity 2‐15J; 40‐360N). Burning tests of two experimental formulations demonstrate potential green pyrotechnic applications. Interestingly, submicron‐counterparts remarkable initiating capability. Considering ease synthesis, safety profile, these materials can be effectively transported microform rapidly converted into submicron‐form on demand, making them suitable

Язык: Английский

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Synthesis and Performance Evaluation of Zwitterionic C–N Bonded Triazole-Tetrazole-Based Primary Explosives

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Сен. 24, 2024

Developing advanced metal-free nitrogen-enriched primary explosives is challenging due to the inherent risks associated with their synthesis and handling. However, there an urgent need develop novel lead-free, nitrogen-rich that offer balanced energetic properties. C-N bonded bicyclic compound 3-azido-1-(1

Язык: Английский

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Skeletal Editing of Energetic Materials: Acid-Catalyzed One-Step Synthesis of Bridged Triazoles as High-Energy-Density Materials via the Nef Reaction

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(47), С. 64929 - 64939

Опубликована: Ноя. 13, 2024

Thermally stable insensitive energetic materials have captivated significant attention from the global research community due to their potential impact. In this study, a series of symmetric and asymmetric nitromethyl-bridged triazole compounds were synthesized pyrimidine moieties via skeletal editing approach. Additionally, carbonyl-bridged in single step by using acid-catalyzed Nef reactions nitromethyl precursors. Peripheral modifications resulted fused moieties. All fully characterized infrared spectroscopy, high-resolution mass spectrometry, multinuclear magnetic resonance elemental analysis, differential scanning calorimetry. Single-crystal X-ray diffraction analysis confirmed structures 4 10. The newly exhibit densities ranging 1.75 1.86 g cm–3, detonation velocities between 8044 8608 m s–1, pressures 23.10 30.31 GPa. Notably, 9 10 demonstrate exceptional heat resistance, with decomposition temperatures 315 335 °C, respectively. Computational studies, including density functional theory, quantum theory atoms molecules, noncovalent interactions, electrostatic surface account for hydrogen-bonding interactions. This work highlights development high-performing, thermally materials.

Язык: Английский

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Advancing Energetic Chemistry: First Synthesis of Sulfur-Based C-C Bonded Thiadiazole-Pyrazine Compounds with Nitrimino Moiety

Dalton Transactions, Год журнала: 2024, Номер 53(48), С. 19112 - 19115

Опубликована: Янв. 1, 2024

Sulfur-based energetic materials 3 to 7 were synthesized considering the limited availability of structural combinations polynitrogen- and oxygen-based organic scaffolds, thereby advancing their limits.

Язык: Английский

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