Combination Multinitrogen with Good Oxygen Balance: Molecule and Synthesis Design of Polynitro-Substituted Tetrazolotriazine-Based Energetic Compounds

Abstract

We investigated 5,8-dinitro-5,6,7,8-tetrahydrotetrazolo[1,5-b][1,2,4]triazine (short for DNTzTr (1)) using various ab initio quantum chemistry methods. We proposed an additional three novel polynitro-substituted tetrazolotriazine-based compounds with exceptional performance, including 5,8-dinitro-5,6-dioxotetrazolo[1,5-b][1,2,4]triazine, DNOTzTr (2), 4,5,9,10-tetranitro[1,2,4,5]tetrazolo[3,4-b][1,2,4,5]tetrazolo[3',4':5,6]triazino[2,3-e]triazine, TNTzTr (3), and 4,5,6,10,11,12-hexanitro-bis[1,2,4,5]tetrazolo[3',4':5,6]triazino[2,3-b:2',3'-e]triazine, HNBTzTr (4). The optimized structure, electronic density, natural bond orbital (NBO) charges and HOMO-LUMO orbitals, electrostatic potential on surface of molecule, IR- and NMR-predicted spectra, as well as thermochemical parameters were calculated with the B3LYP/6-311+G(2d) level of theory. Critical parameters such as density, enthalpy of formation (EOF), and detonation performance have also been predicted. Characters with positive EOF (1386.00 and 1625.31 kJ/mol), high density (over 2.00 g/cm(3)), outstanding detonation properties (D = 9.82 km/s, P = 45.45 GPa; D = 9.94 km/s, P = 47.30 GPa), the perfect oxygen balance set to zero, and acceptable impact sensitivity led novel compounds 3 and 4 to be very promising energetic materials. This work provides the theoretical molecule design and a reasonable synthesis path for further experimental synthesis and testing.

Exploration of High‐Energy‐Density Materials: Computational Insight into Energetic Derivatives Based on 1,2,4,5‐Tetrahydro‐1,2,4,5‐tetrazine

“…Electronic density is a fundamental indicator that can express various physical and chemical properties of an energetic material . The contour line maps of the electronic densities on compounds A4 and B4 are visualized in Figure .…”

Energetic Salts Based on Tetrazole N‐Oxide

“…The often restricted time cost and danger associated with the synthesis and testing of an energetic material have driven the advancement of computationally assisted design and prediction of new HEDMs . The improved properties confirm that oxidation of tetrazoles to tetrazole oxides is indeed an effective method of improving energetic performance.…”

Crystal Structure and Properties of 7‐Imino‐3‐Nitroimino‐2,4,6,8‐Tetraazabicyclo[3.3.0]Octane Hydrochloride

“…The critical temperature of thermal explosion (T b ) is an important parameter to evaluate the thermal stability of an energetic compound because it is essential to insure the safe storage and process operations involving explosives, propellants, and pyrotechnics. [20,21] The value of T b of 558.5 K can be calculated by the following Equation (8): [22] T b = (E 0 -ΊE 0 2 -4E 0 RT p0 ) / 2R (8) where E 0 is the apparent activation energy obtained by Ozawa's method, R is the gas constant, and T p0 is the peak temperature corresponding to βǞ0, 551.3 K. The distribution of electronic density is an important indicator to express the chemical and physical properties of a molecule, [23] and the contour line map of the electronic density on compound A was drawn in Figure 4 using the Multiwfn program. [24] It is reported that heavy nucleus always possess high peaks due to the nuclear charge improving electron aggregation and then displays integral exponential attenuation towards all surrounding atoms.…”