Theoretical studies on a new high energy density compound 6-amino-7-nitropyrazino[2,3-e][1,2,3,4]tetrazine 1,3,5-trioxide (ANPTTO)

Abstract

The derivatives of 1,2,3,4-tetrazine may be promising candidates for high-energy density compounds and are receiving more and more attentions. In this study, a new derivative 6-amino-7-nitropyrazino[2,3-e][1,2,3,4]tetrazine 1,3,5-trioxide (ANPTTO) has been designed. The geometrical structure and IR spectrum in the gas phase were studied at the B3LYP/6-31G* level of density functional theory (DFT). The crystal structure was predicted by molecular mechanics method and refined by the GGA/BOP function of periodic DFT with the basis set of TNP. The gas phase enthalpy of formation was calculated by the homodesmotic reaction method. The enthalpy of sublimation and solid phase enthalpy of formation were also predicted. The detonation properties were estimated with the Kamlet-Jacobs equations based on the predicted density and enthalpy of formation in solid state. The available free space in the lattice and resonance energy were calculated to evaluate its stability. ANPTTO has a high stability and is a promising high energetic component with the density >2 g · cm(-3), detonation velocity >9000 m · s(-1), and detonation pressure >40 GPa. A synthetic route was proposed to provide a consideration for further study.

Novel Nitrogen‐Rich Tetrazine‐Based High Energy Density Molecules: Molecular Design and Computational Studies

“…The oxidation of 1 with strong oxidizing reagent, e. g., hypofluorous acid can lead to the formation of oxidized 3amine-6-nitro-1,2,4,5-tetrazine derivative 2 a-d [19,[30][31][32]. Compounds 2 a-d are also accessible from oxidized 1,2,4,5tetrazine-3,6-diamine 1', obtained through peroxytrifluoroacetic acid mediated oxidation of 1 (Scheme 1a) [32][33][34].…”

“…Moreover, the consistent quest of new highly efficient HEDMs has attracted chemists over the last three decades [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19]. Generally, 'high energy' and 'density' have been prime concern towards synthesizing HEDMs [2,9,[10][11][12][13][14][15][16][17]20] and it can be modified by structural manipulation of molecules [1,3,4,5,7,8,18,19]. In this regard, theoretical studies provide an outstanding platform to anticipate the properties of HEDMs, which in turn help to design better and efficient molecules.…”

Synthesis and Luminescent Properties of s-Tetrazine Derivatives Conjugated with the 4H-1,2,4-Triazole Ring

“…This unique ring contains four nitrogen atoms, which is the maximum content in a stable six-membered system. This specific structure has attracted scientists’ attention as an important candidate for high energy density materials (HEDMs, A, Scheme 1 ), as its thermal decomposition leads to ring opening and the release of a nitrogen molecule [ 1 , 2 , 3 ]. The high nitrogen content has also encouraged research into its biological activity (B, Scheme 1 ), which has resulted in compounds that have anti-tubercular, anti-cancer, or anti-malarial effects [ 4 , 5 , 6 ].…”

Synthesis and anticancer activity evaluation of some new 1,2,3,5-tetrazine derivatives attached to benzothiazole moiety

“…[3][4][5] Nitrogen-rich heterocyclic molecules particularly those of the tetrazine groups (sixmembered ring with four nitrogen atoms) are used in material sciences to make high density energy compounds, because their thermal decomposition leads to the ring opening, resulting in the formation of nitriles and nitrogen molecules. [6][7][8] Additionally, synthetic tetrazine derivatives have been used in molecular imaging. Examples included targeted labelling, delivery of radionuclide, and visualization of tumors in lung cells and mice; fluorescent label proteins on the surface and inside mammalian cells, [9][10][11][12] and covalent bonding of tetrazine molecules to the surface of cells to study cell-to-cell interactions 13 .…”