Molecular design of energetic tetrazine-triazole derivatives

Journal of Molecular Modeling volume 27, Article number: 98 (2021) Cite this article

Abstract

Nitrogen-rich compounds are promising candidates for preparing high energetic density materials (HEDMs) and show the potential in the application of propellants, explosives, and pyrotechnics. Two kinds of typical nitrogen-rich compounds, such as tetrazine and triazole, have attracted the attentions in recent years owing to their high densities, good thermal stabilities, and excellent energetic performances. In this work, four series of innovative energetic compounds based on the conjugates of tetrazine and triazole bearing various substituents (–NH2, –NO2, and –NHNO2) were designed. The optimized structures, crystal densities, heats of formation (HOFs) in gas phase and in condensed phase, detonation properties, bond dissociation energies (BDEs), and impact sensitivity (h50) of these compounds were studied systematically via density functional theory (DFT) method. The detonation velocities of four series of compounds are in the range between 7.03 and 8.59 km s−1 and their detonation pressures are in the range between 20.6 and 33.1 GPa. Results indicated that the linkage of –N=N– bond contributed significantly to HOFs and energy density of the energetic molecules, and 1,2,3-triazole showed better performances than 1,2,4-triazole slightly. As for the same series compounds with different substituents, the compounds with –NHNO2 possessed the highest HOFs (such as A6, B6, C6, D6). In terms of the energetic properties (D and P), four compounds (A7, B7, C7, and D7) exhibited the comparable performance with the widely used hexa-hydro-1,3,5-trinitro-1,3,5-triazine (RDX) and in the meanwhile displayed superior thermal stability and sensitivity to RDX, which indicated their potential application in the insensitive energetic materials.

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Funding

The project was supported by Beijing Institute of Technology (2018CX10002).

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Affiliations

  1. School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China

    Yi Li, Yanyue Li, Shaohua Jin, Shengfu Li, Kun Chen & Fang Bao

Authors
  1. Yi Li
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  2. Yanyue Li
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  3. Shaohua Jin
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  4. Shengfu Li
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  5. Kun Chen
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  6. Fang Bao
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Contributions

Li Yi contributed to the conception of the study, performed the experiment and wrote the manuscript; Li Shengfu helped perform the data analyses; Chen Kun and Jin Shaohua contributed significantly to analysis; Chen Kun, Li Yanyue, and Bao Fang helped perform the analysis with constructive discussions.

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Correspondence to Kun Chen or Fang Bao.

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Li, Y., Li, Y., Jin, S. et al. Molecular design of energetic tetrazine-triazole derivatives. J Mol Model 27, 98 (2021). https://doi.org/10.1007/s00894-021-04714-3

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Keywords

  • Nitrogen-rich compounds
  • HEDMs
  • Tetrazine
  • Triazole
  • Density functional theory
  • Explosives