Energetic Salts Based on 3,5-Bis(dinitromethyl)-1,2,4-triazole Monoanion and Dianion: Controllable Preparation, Characterization, and High Performance

Journal of the American Chemical Society, Journal Year: 2016, Volume and Issue: 138(24), P. 7500 - 7503

Published: June 6, 2016

Molecular modification of known explosives is considered to be an efficient route design new energetic materials. A family salts based on the 3,5-bis(dinitromethyl)-1,2,4-triazole monoanion and dianion were controllably synthesized by using 1-diamino-2,2-dinitroethene as a precursor. X-ray structure determination monohydrazinium 3,5-bis(dinitromethyl)-1,2,4-triazolate (5) monoammonium (6) diammonium hydrate (8·H2O) further confirmed structures these anions. In addition, supported data, in system, roving proton ring nitrogen rather than gem-dinitro carbon results extensive hydrogen-bonding interactions higher packing coefficients. Interestingly, 5 6 possess highest calculated crystal densities, 1.965 1.957 g cm(-3) at 150 K, for hydrazinium ammonium salts, respectively. Energetic evaluation indicates that (detonation velocity vD = 9086 m s(-1); detonation pressure P 38.7 GPa) (vD, 9271 41.0 exhibit great properties, superior those current highly explosive benchmarks, such 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX).

Language: Английский

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1,2,5‐Oxadiazole‐Based High‐Energy‐Density Materials: Synthesis and Performance

ChemPlusChem, Journal Year: 2019, Volume and Issue: 85(1), P. 13 - 42

Published: Oct. 16, 2019

Abstract This Review covers the synthesis and performance of most promising 1,2,5‐oxadiazole‐based high‐energy density materials (HEDMs). These comprise a 1,2,5‐oxadiazole subunit as key structural motif linked to various acyclic explosophoric groups or nitrogen‐rich nitrogen‐oxygen azoles: 1,2,4‐triazole, tetrazole, 1,2,4‐ 1,3,4‐oxadiazoles. Energetic alliances two more rings directly through heteroatom spacers are also presented. Particular attention is devoted installation different explosophores: nitro, nitramino, azo, azoxy, dinitromethyl, trinitroethyl moieties their combination. Promising environmentally benign energetic with high detonation velocity pressure, outstanding insensitivity summarized. Overall, presented may be considered next‐generation high‐performance that superior commonly used traditional explosives (TNT, PETN, RDX, HMX).

Language: Английский

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Novel 1,2,4-Oxadiazole Derivatives in Drug Discovery

Pharmaceuticals, Journal Year: 2020, Volume and Issue: 13(6), P. 111 - 111

Published: May 29, 2020

Five-membered 1,2,4-oxadiazole heterocyclic ring has received considerable attentionbecause of its unique bioisosteric properties and an unusually wide spectrum biological activities.Thus, it is a perfect framework for the novel drug development. After century since the1,2,4-oxadiazole have been discovered, uncommon potential attracted medicinal chemists'attention, leading to discovery few presently accessible drugs containing 1,2,4-oxadiazoleunit. It worth noting that interest in 1,2,4-oxadiazoles' application doubledin last fifteen years. Herein, after concise historical introduction, we present comprehensiveoverview recent achievements synthesis 1,2,4-oxadiazole-based compounds themajor advances their applications period five years as well briefremarks on prospects further

Language: Английский

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Conjugated Energetic Salts Based on Fused Rings: Insensitive and Highly Dense Materials

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(44), P. 15001 - 15007

Published: Oct. 17, 2018

Nitroamino-functionalized 1,2,4-triazolo[4,3- b][1,2,4,5]tetrazine (1), when combined with intermolecular hydrogen bonds (HBs) and strong noncovalent interactions between layers, results, for example, in an interlayer distance of 2.9 Å dihydroxylammonium 3,6-dinitramino-1,2,4-triazolo[4,3- (2c) a packing coefficient 0.805. For 6,6'-dinitramino-3,3'-azo-1,2,4-triazolo[4,3- (3b), two fused rings are linked by azo group, which expands the conjugated system resulting even shorter 2.7 higher 0.807. These values appear to be shortest distances highest coefficients reported tetrazine energetic materials. With high coefficients, both possess densities 1.92 g cm-3 1.99 at 293 K, respectively. Compared its precursor, hydroxylammonium moiety serves as buffer chain (H-N-O-H), connecting anion cation through bonds, giving rise more favorable stacking, density lower sensitivity. The sensitivities all salts than that their neutral precursors, such compound 2 (3 J, >5 N) 2c (25 360 N). detonation properties (detonation velocity vD = 9712 m s-1 pressure P 43 GPa) 3b (vD 10233 s-1; 49 exceed those present explosive benchmarks, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) hexanitrohexaazaisowurzitane (CL-20). molecular structures several these new materials confirmed single-crystal X-ray diffraction measurements. Using calculated experimental ring planar large π-conjugated results compromise desirable stabilities properties, thus enhancing future utilization design

Language: Английский

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Taming Dinitramide Anions within an Energetic Metal–Organic Framework: A New Strategy for Synthesis and Tunable Properties of High Energy Materials

Chemistry of Materials, Journal Year: 2016, Volume and Issue: 28(5), P. 1472 - 1480

Published: Feb. 5, 2016

Energetic polynitro anions, such as dinitramide ion [N(NO2)2–], have attracted significant interest in the field of energetic materials due to their high densities and rich oxygen contents; however, most them usually suffer from low stability. Conveniently stabilizing anions develop new energy well tuning properties still represent challenges. To address these challenges, we herein propose a novel strategy that are encapsulated within cationic metal–organic frameworks (MOFs). We present N(NO2)2– three-dimensional (3D) MOF through simple anion exchange. The resultant inclusion complex exhibits remarkable thermal stability with onset decomposition temperature 221 °C, which is, our knowledge, highest value known for all dinitramide-based compounds. In addition, it possesses good properties, can be conveniently tuned by changing mole ratio starting materials. also released controlled fashion without disrupting framework. This work may shed insights into stabilization, storage, release labile under ambient conditions, while providing convenient approach preparation MOFs modulation properties.

Language: Английский

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Pushing the Limits of Oxygen Balance in 1,3,4-Oxadiazoles

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(26), P. 8816 - 8819

Published: June 19, 2017

Gem-trinitromethyl groups were introduced into a 1,3,4-oxadiazole ring to give the first example of bifunctionalized single five-membered with six nitro groups. 2,5-Bis(trinitromethyl)-1,3,4-oxadiazole (12) has high calculated crystal density 2.007 g cm-3 at 150 K (1.941 293 K) and very positive oxygen balance (39.12%), which makes it strong candidate as energy dense oxidizer. The dihydroxylammonium dihydrazinium salts bis(trinitromethyl)-1,3,4-oxadiazole (5 6) exhibit excellent detonation properties (5, vD = 9266 m s-1, P 38.9 GPa; 6, 8900 36.3 GPa) acceptable impact sensitivities 20 J, 6 19 J), are superior those RDX (7.4 J) HMX J). Such attractive features support application potential gem-polynitromethyl group in design advanced energetic materials. Surprisingly, 2,5-bis(trinitromethyl)-1,3,4-oxadiazole is more thermally stable less sensitive than its bis(dinitromethyl) analogue, 8.

Language: Английский

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Assembly of Tetrazolylfuroxan Organic Salts: Multipurpose Green Energetic Materials with High Enthalpies of Formation and Excellent Detonation Performance

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 25(16), P. 4225 - 4233

Published: Jan. 15, 2019

A series of highly energetic organic salts comprising a tetrazolylfuroxan anion, explosophoric azido or azo functionalities, and nitrogen-rich cations were synthesized by simple, efficient, scalable chemical routes. These materials fully characterized IR multinuclear NMR (1 H, 13 C, 14 N, 15 N) spectroscopy, elemental analysis, differential scanning calorimetry (DSC). Additionally, the structure an salt consisting azidotetrazolylfuroxan anion 3,6,7-triamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazolium cation was confirmed single-crystal X-ray diffraction. The compounds exhibit good experimental densities (1.57-1.71 g cm-3 ), very high enthalpies formation (818-1363 kJ mol-1 and, as result, excellent detonation performance (detonation velocities 7.54-8.26 kms-1 pressures 23.4-29.3 GPa). Most have moderate sensitivity toward impact friction, which makes them promising candidates for variety applications. At same time, three on primary explosives level (1.5-2.7 J). results along with parameters nitrogen contents (66.0-70.2 %) indicate that these may serve potential environmentally friendly alternatives to lead-based explosives.

Language: Английский

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1,3,4‐Oxadiazole Bridges: A Strategy to Improve Energetics at the Molecular Level

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(10), P. 5497 - 5504

Published: Dec. 5, 2020

Abstract Many energetic materials synthesized to date have limited applications because of low thermal and/or mechanical stability. This limitation can be overcome by introducing structural modifications such as a bridging group. In this study, series 1,3,4‐oxadiazole‐bridged furazans was prepared. Their structures were confirmed 1 H and 13 C NMR, infrared, elemental, X‐ray crystallographic analyses. The stability, friction sensitivity, impact detonation velocity, pressure evaluated. hydroxylammonium salt 8 has an excellent performance ( D =9101 m s −1 , P =37.9 GPa) insensitive properties (IS=17.4 J, FS=330 N), which show its great potential high‐performance explosive. Using quantum computation crystal structure analysis, the effect introduction 1,3,4‐oxadiazole moiety on molecular reactivity difference between sensitivities stabilities mono‐ bis‐1,3,4‐oxadiazole bridges are considered. synthetic method for systematic study compounds provide theoretical basis future energetics design.

Language: Английский

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High performance and heat-resistant pyrazole-1,2,4-triazole energetic materials: Tuning the thermal stability by asymmetric framework and azo-bistriazole bridge

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 433, P. 134480 - 134480

Published: Jan. 6, 2022

Language: Английский

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Facile synthesis of nitroamino-1,3,4-oxadiazole with azo linkage: a new family of high-performance and biosafe energetic materials

Journal of Materials Chemistry A, Journal Year: 2022, Volume and Issue: 10(42), P. 22803 - 22811

Published: Jan. 1, 2022

Energetic materials serve as remarkable fuel/propellants for space shuttles, and their utility in civil military applications is vast.

Language: Английский

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