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Molecular design of long intra‐annular nitrogen chains: 3H‐tetrazolo[1,5‐d]tetrazole‐based high‐energy‐density materials
Author(s) -
Zhao Xiuxiu,
Zhang Yingchao,
Xie Congxia,
Tan Long
Publication year - 2021
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26743
Subject(s) - tetrazole , detonation , chemistry , nitrogen , substituent , thermal decomposition , detonation velocity , thermal stability , energetic material , computational chemistry , density functional theory , standard enthalpy of formation , kinetic energy , organic chemistry , explosive material , physics , quantum mechanics
Energetic compounds containing long nitrogen chain, have been a research hotspot. Fused heterocycles are stable due to their aromatic systems. Compounds obtained by combining long nitrogen chain and fused ring can not only retain good energetic property, but also ensure better stability. In this work, eight fused heterocycle‐based energetic compounds, 3H‐tetrazolo[1,5‐d]tetrazole ( 1 ) and its derivatives ( 2 – 8 ), were designed, containing a nitrogen chain with seven nitrogen atoms. The HOF, thermal stability, and energetic properties of these compounds were studied using the DFT method. The results show that the introduction of –NO 2 , –N 3 , –NF 2 , –ONO 2 , and –NHNO 2 groups greatly increased the density, HOF, detonation velocity, and detonation pressure. The densities of 3 , 5 , 7 , and 8 fall within the range designated for high‐energy‐density materials. The calculated detonation velocities of the compounds 3 and 8 are as high as 9.86 and 9.78 km s −1 , which are superior to that of CL‐20. Kinetic study of the thermal decomposition mechanism indicates that the N–R bonds may not be the weakest bonds in these compounds. The tetrazole ring opening of the heterocycle‐based energetic compounds, followed by N 2 elimination, is predicted to be the primary decomposition channel, regardless of whether substituent groups are present.