Bistriazolotriazole-tetramine: commendable energetic moiety and cation

Rimpi Devi; Kalpana Sharma; Vikas D Ghule; Srinivas Dharavath

doi:10.1007/s00894-024-05892-6

Bistriazolotriazole-tetramine: commendable energetic moiety and cation

J Mol Model. 2024 Mar 9;30(4):98. doi: 10.1007/s00894-024-05892-6.

Authors

Rimpi Devi¹, Kalpana Sharma¹, Vikas D Ghule², Srinivas Dharavath³

Affiliations

¹ Department of Chemistry, National Institute of Technology Kurukshetra, Kurukshetra, 136119, Haryana, India.
² Department of Chemistry, National Institute of Technology Kurukshetra, Kurukshetra, 136119, Haryana, India. gvd@nitkkr.ac.in.
³ Energetic Materials Laboratory, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, Uttar Pradesh, India.

PMID: 38461222
DOI: 10.1007/s00894-024-05892-6

Abstract

Context: Various 7H,7'H-[6,6'-bi[1,2,4]triazolo[4,3-b][1,2,4]triazole]-3,3',7,7'-tetramine (A) based nitrogen-rich energetic salts were designed and their properties explored. All energetic salts possess relatively high nitrogen content (> 48%), positive heats of formation (> 429 kJ/mol) and stability owing to a significant contribution from fused backbone. The cationic component shows a very high heat of formation (2516 kJ/mol); therefore, it is highly suitable for enthalpy enhancement in new energetic salts. The cation was paired with the energetic anions nitrate (NO₃^-), perchlorate (ClO₄^-), dinitromethanide (CH(NO₂)₂^-), trinitromethanide (C(NO₂)₃^-), nitroamide (NHNO₂^-), and dinitroamide (N(NO₂)₂^-) to improve oxygen balance and detonation performance. Designed salts show moderate detonation velocities (7.9-8.7 km/s) and pressures (23.8 - 33.1 GPa). The distribution of frontier molecular orbitals, molecular electrostatic surface potentials, QTAIM topological properties, and noncovalent interactions of designed salts were simulated to understand the electronic structures, charge distribution in molecules, hydrogen bonding, and other nonbond interactions. The predicted safety factor (SF) and impact sensitivity (H₅₀) of designed salts suggest their insensitivity to mechanical stimuli. This work explored the 7H,7'H-[6,6'-bi[1,2,4]triazolo[4,3-b][1,2,4]triazole]-3,3',7,7'-tetramine as a suitable cationic component which could be promising and serve exemplarily in energetic materials.

Methods: The optimization and energy calculations of all the designed compounds were carried out at the B3LYP/6-311 + + G(d,p) and M06-2X/def2-TZVPP levels, utilizing the Gaussian software package. The molecular surface electrostatic potential, quantum theory of atoms in molecules (QTAIM), reduced density gradient (RDG), and noncovalent interaction (NCI) analysis were performed by employing Multiwfn software. The EXPLO5 (v 7.01) thermochemical code and PILEM web application were used to predict the detonation properties.

Keywords: Detonation; Energetic materials; Fused backbone; Heat of formation; QTAIM.