Synthesis and detonation performance of novel tetrazolyl–triazine nitrogen-rich energetic materials

A new series of high energy density materials were synthesized by combining the oxalyldihydrazinium (H 2 ODH 2+ ) dication with 5,5′-tetranitro-2,2′-bi-1H-imidazolate (TNBI 2− ), 5,5′diamino-4,4′-dinitramino-3,3′-bi-1,2,4-triazolate (ANAT 2− ) and bis [3-(5-nitroimino-1,2,4-triazolate)] (BNT 2− ) dianions. These materials were fully characterized by nuclear magnetic resonance ( 1 H and 13 C) and infrared spectroscopy, gas pycnometry, thermogravimetric analysis and differential scanning calorimetry. In addition, the crystal structures of the energetic salts [H 2 ODH]-[TNBI] and [H 2 ODH][ANAT] were determined by single-crystal X-ray diffraction. Thermal analysis revealed decomposition temperatures of 183 °C for [H 2 ODH][ANAT], 200 °C for [H 2 ODH]-[TNBI] and 209 °C for [H 2 ODH][BNT], while the densities of these salts were determined to be 1.82, 1.91, and 1.94 g cm −3 , respectively. The structural features of these new energetic salts revealed π-stacking and hydrogen-bonding interactions, which contribute to the close packing and associated high densities. All salts exhibited high detonation properties (detonation pressure: 39.2−43.7 GPa; detonation velocity: 9246−9783 m s −1 ), which are superior or similar to those of benchmark explosives such as 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7tetranitro-1,3,5,7-tetrazocine (HMX).

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Dissociation Without Detonation: A DFT Analysis of the Thermally Induced Fragmentation of Binary Sulfur–Nitrogen Rings and Cages

Chivers,

Oakley

2024

Inorg. Chem.

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Potential thermal dissociation pathways available to binary sulfur nitrides have been explored by density functional theory methods, and the results interpreted in terms of their known thermochemical behavior. The cyclic cation/anion pair S 3 N 3 ± both undergo concerted (4 + 2) cycloreversions to afford the 3membered thiadiazirine ring c-NSN and, respectively, the SNS ± cation/anions. A similar pathway has been identified for S 4 N 2 , leading to S 3 and c-NSN. More complex multistep routes for the elimination of c-NSN have been identified for the bicyclic cation/ anion pair S 4 N 5 ± , as well as for the neutral cage structures S 4 N 4 and S 5 N 6 . For the S 4 N 5 + cation a transition state for competing skeletal scrambling via a 1,3-nitrogen σ-bond shift has been located. For the multiply charged cations S 3 N 2 2+ and S 4 N 4 2+ , dissociation mechanisms are driven by charge repulsion effects, affording SNS + /SN + and S 3 N 3 + /SN + respectively. Channels leading to loss of NS + from the cyclic cation species S 4 N 3 + and S 5 N 5 + have also been examined, and the possible role of open-chain and cyclic S 3 N 2based intermediates in the formation of S 2 N 2 during the thermal cracking of S 4 N 4 over silver wool is explored.

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Synthesis and detonation performance of novel tetrazolyl–triazine nitrogen-rich energetic materials

Abstract: The properties of energetic materials (EMs) are significantly influenced by specific features of their components and including multiple nitrogen-rich (N-rich) heterocycles within a single rigid framework is perhaps one of...

Cited by 3 publications

References 51 publications

Triazines, tetrazines, and fused ring polyaza systems

Triazines, tetrazines, and fused ring polyaza systems

Unleashing Ultrahigh Detonation Performance with Oxalyldihydrazinium Dication-Based Energetic Salts

Dissociation Without Detonation: A DFT Analysis of the Thermally Induced Fragmentation of Binary Sulfur–Nitrogen Rings and Cages

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