Properties and Promise of Catenated Nitrogen Systems As High-Energy-Density Materials

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(12), P. 5682 - 5744

Published: June 16, 2020

The properties of catenated nitrogen molecules, molecules containing internal chains bonded atoms, is fundamental scientific interest in chemical structure and bonding, as uniquely situated the periodic table to form kinetically stable compounds often with chemically N–N bonds but which are thermodynamically unstable that formation multiply N2 usually preferable. This unique placement makes for development high-energy-density materials, including explosives defense construction purposes, well propellants missile propulsion space exploration. review, designed a audience, describes foundational subjects, methods, metrics relevant energetic materials community provides an overview important classes ranging from theoretical investigation hypothetical practical application real-world materials. review intended provide detailed insight into synthesis decomposition such knowledge science new most chemists.

Language: Английский

---

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

---

Tri-explosophoric groups driven fused energetic heterocycles featuring superior energetic and safety performances outperforms HMX

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 28, 2022

The design and synthesis of novel energetic compounds with integrated properties high density, energy, good thermal stability sensitivities is particularly challenging due to the inherent contradiction between energy safety for compounds. In this study, a structure 4-amino-7,8-dinitropyrazolo-[5,1-d] [1,2,3,5]-tetrazine 2-oxide (BITE-101) designed synthesized in three steps. With help complementary advantages different explosophoric groups diverse weak interactions, BITE-101 superior benchmark explosive HMX all respects, including higher density 1.957 g·cm

Language: Английский

---

Azo-linked high-nitrogen energetic materials

Journal of Materials Chemistry A, Journal Year: 2017, Volume and Issue: 6(5), P. 1915 - 1940

Published: Dec. 22, 2017

In this review, we document the most recent developments in azo-linked heteroaromatic (imidazole, pyrazole, triazole, triazine, tetrazine and oxadiazole) high-nitrogen energetic materials their salts.

Language: Английский

---

Synthesis of Tetrazino‐tetrazine 1,3,6,8‐Tetraoxide (TTTO)

Angewandte Chemie International Edition, Journal Year: 2016, Volume and Issue: 55(38), P. 11472 - 11475

Published: July 20, 2016

Abstract This study presents the first synthesis and characterization of a new high energy compound [1,2,3,4]tetrazino[5,6‐e][1,2,3,4]tetrazine 1,3,6,8‐tetraoxide (TTTO). It was synthesized in ten steps from 2,2‐bis( tert ‐butyl‐ NNO ‐azoxy)acetonitrile. The synthetic strategy based on sequential closure two 1,2,3,4‐tetrazine 1,3‐dioxide rings by generation oxodiazonium ions their intramolecular coupling with ‐azoxy groups. TTTO structure confirmed single‐crystal X‐ray.

Language: Английский

---

Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids

Frontiers in Chemistry, Journal Year: 2018, Volume and Issue: 6

Published: March 15, 2018

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design new functionalized ILs. dicyanamide (DCA) ILs are typical CHN type which halogen free, chemical stable, low-viscous and fuel-rich. transport properties DCA significant for their applications as solvents, electrolytes hypergolic propellants. This work systematically investigates several important four ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], N8444[N(CN)2]) including viscosity, conductivity, electrochemical property at different temperatures. melting points, temperature-dependent viscosities conductivities reveal the structure-activity relationship From Walden plots, imidazolium cations exhibit stronger cation–anion attraction than ammonium cations. have relatively high values windows (EWs), indicates that potential candidates in applications. cyclic voltammograms Eu(III) these GC working electrode various temperatures 303–333 K consists quasi-reversible waves. also dominated by cationic structures. current intensity (ip), diffusion coefficients (Do), charge transfer rate constants (ks) all increased with molar increased. structure-transport were constructed designing novel fulfill specific demands.

Language: Английский

---

Developments towards synthesis of N-heterocycles from amidinesviaC–N/C–C bond formation

Organic Chemistry Frontiers, Journal Year: 2019, Volume and Issue: 6(13), P. 2120 - 2141

Published: Jan. 1, 2019

This review focuses on the synthesis of N-heterocycles using amidines as starting materials, with an emphasis mechanisms these reactionsviaC–N/C–C bond formation.

Language: Английский

---

3,6‐Dinitropyrazolo[4,3‐c]pyrazole‐Based Multipurpose Energetic Materials through Versatile N‐Functionalization Strategies

Angewandte Chemie International Edition, Journal Year: 2016, Volume and Issue: 55(41), P. 12895 - 12897

Published: Sept. 15, 2016

Abstract A family of 3,6‐dinitropyrazolo[4,3‐c]pyrazole‐based energetic compounds was synthesized by using versatile N ‐functionalization strategies. Subsequently, nine ionic derivatives the , N′ ‐(3,6‐dinitropyrazolo[4,3‐c]pyrazole‐1,4‐diyl)dinitramidate anion were prepared acid‐base reactions and fully characterized infrared, multinuclear NMR spectra, elemental analysis. The structures four these further confirmed single‐crystal X‐ray diffraction. Based on their different physical detonation properties, exhibit promising potential as modern materials can be variously classified green primary explosives, high‐performance secondary fuel‐rich propellants, propellant oxidizers.

Language: Английский

---

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

---

Pursuing reliable thermal analysis techniques for energetic materials: decomposition kinetics and thermal stability of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50)

Physical Chemistry Chemical Physics, Journal Year: 2016, Volume and Issue: 19(1), P. 436 - 449

Published: Nov. 10, 2016

Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) was studied using number thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate ARC). To obtain more comprehensive insight into the kinetics mechanism TKX-50 decomposition, variety complementary thermoanalytical experiments were performed under various conditions. Non-isothermal isothermal obtained at both atmospheric low (up to 0.3 Torr) pressures. The gas products thermolysis detected in situ IR spectroscopy, structure solid-state determined by X-ray diffraction electron microscopy. Diammonium (ABTOX) directly identified be most important intermediate process. role bistetrazole diol (BTO) also rationalized with mixtures BTO. Several widely used data processing (Kissinger, isoconversional, formal kinetic approaches, etc.) independently benchmarked against ARC data, which are germane real storage application conditions energetic materials. Our study revealed that none Arrhenius parameters reported before can properly describe complex two-stage process TKX-50. In contrast, we showed superior performance isoconversional methods combined measurements, yielded reliable thermolysis. contrast existing reports, stability lower than hexogen, but close hexanitrohexaazaisowurtzitane (CL-20).

Language: Английский

---