Theoretical investigations on azole-fused tricyclic 1,2,3,4-tetrazine-2-oxides.

Fused compounds, a unique class of large conjugate structures, have emerged as prime candidates over traditional nitrogen-rich mono-ring or poly-ring materials. Meanwhile, compounds containing catenated nitrogen chains have also attracted attention from scientists due to their high heats of formation. On the other hand, the azoxy [-N[double bond, length as m-dash]N(O)-] moiety has been found to increase density effectively in the molecular structure of compounds. Therefore, combining fused heterocyclic organic skeletons with the azoxy moiety can be regarded as an effective method for increasing the density and heat of formation, which results in substantial increase in detonation properties. Based on the above-mentioned considerations, in this study, a series of new non-hydrogen-containing 5/6/5 fused ring molecules with azoxy moiety structures are designed. Furthermore, their properties as potential high-energy-density materials, including their density, heats of formation, detonation properties, and impact sensitivity, have been extensively evaluated using thermodynamic calculations and density functional theory. Among the investigated compounds, 1,3,8,10-tetranitrodiimidazo[1,5-:5',1'-][1,2,3,4]tetrazine 5-oxide (B), 1,10-dinitrobis([1,2,3]triazolo)[1,5-:5',1'-][1,2,3,4]tetrazine 5-oxide (C) and 2,9-dinitrobis([1,2,4]triazolo)[1,5-:5',1'-][1,2,3,4]tetrazine 5-oxide (D) display remarkable stabilities and are predicted to be high-performance energetic materials due to their high density (>1.94 g cm), detonation velocity (>9616 m s), and detonation pressure (>41.1 GPa). In addition, our design strategy, which combines the azoxy moiety and fused tricyclic skeleton to construct nitrogen-rich molecular structures with high density and positive heat of formation, is a valuable approach for developing novel high-energy-density materials with excellent performance and stability.