TY - JOUR
T1 - Unlocking the effect of monocyclic and fused backbones on energy and stability of fully nitrated compounds
AU - Jiang, Zhiyi
AU - Ding, Ning
AU - Sun, Qi
AU - Zhao, Chaofeng
AU - Tian, Baojing
AU - Li, Shenghua
AU - Pang, Siping
N1 - Publisher Copyright:
© 2023 Elsevier B.V.
PY - 2023/10/1
Y1 - 2023/10/1
N2 - Despite their attractive energetic performances, fully nitrated monocyclic and fused compounds exhibit varying densities and stabilities. In this context, to reveal the effect of monocyclic and fused backbones on density and stability, two fully nitrated compounds, 1-trinitromethyl-3,5-dinitro-1,2,4-triazole (4) and 3,6-dinitro-7-(trinitromethyl)-[1,2,4]triazolo[4,3-b][1,2,4]trizole (8, BITE-203), with the same groups but different backbones were designed and synthesized via a simple three-step procedure. Experimental results, X-ray diffraction analysis, and quantum calculations indicated that fused BITE-203 exhibits a higher density (1.968 g cm−3 at 296 K) than monocyclic 4 (1.958 g cm−3 at 296 K), which is caused by the stronger intermolecular p-π interactions and closer molecular stacking of BITE-203. In addition, BITE-203 also shows higher stability (168 °C) than 4 (143 °C) owing to its weaker intramolecular repulsion and stronger aromaticity, thus revealing the positive effect of the fused backbone on density and stability enhancement. In addition, BITE-203 is the only trinitromethyl compound that simultaneously achieves a density greater than 1.950 g cm−3 and a thermal decomposition temperature exceeding 165 °C, in addition to a considerable detonation velocity of 9199 m s−1 and high oxygen balance of + 27.6%, demonstrating its excellent potential as a promising high-energy–density material.
AB - Despite their attractive energetic performances, fully nitrated monocyclic and fused compounds exhibit varying densities and stabilities. In this context, to reveal the effect of monocyclic and fused backbones on density and stability, two fully nitrated compounds, 1-trinitromethyl-3,5-dinitro-1,2,4-triazole (4) and 3,6-dinitro-7-(trinitromethyl)-[1,2,4]triazolo[4,3-b][1,2,4]trizole (8, BITE-203), with the same groups but different backbones were designed and synthesized via a simple three-step procedure. Experimental results, X-ray diffraction analysis, and quantum calculations indicated that fused BITE-203 exhibits a higher density (1.968 g cm−3 at 296 K) than monocyclic 4 (1.958 g cm−3 at 296 K), which is caused by the stronger intermolecular p-π interactions and closer molecular stacking of BITE-203. In addition, BITE-203 also shows higher stability (168 °C) than 4 (143 °C) owing to its weaker intramolecular repulsion and stronger aromaticity, thus revealing the positive effect of the fused backbone on density and stability enhancement. In addition, BITE-203 is the only trinitromethyl compound that simultaneously achieves a density greater than 1.950 g cm−3 and a thermal decomposition temperature exceeding 165 °C, in addition to a considerable detonation velocity of 9199 m s−1 and high oxygen balance of + 27.6%, demonstrating its excellent potential as a promising high-energy–density material.
KW - Energy
KW - Fully nitrated compounds
KW - Mechanism investigation
KW - Monocyclic and fused backbones
KW - Stability
UR - http://www.scopus.com/inward/record.url?scp=85172442474&partnerID=8YFLogxK
U2 - 10.1016/j.cej.2023.145331
DO - 10.1016/j.cej.2023.145331
M3 - Article
AN - SCOPUS:85172442474
SN - 1385-8947
VL - 473
JO - Chemical Engineering Journal
JF - Chemical Engineering Journal
M1 - 145331
ER -