Skeletal Editing of Energetic Materials: Acid-Catalyzed One-Step Synthesis of Bridged Triazoles as High-Energy-Density Materials via the Nef Reaction

Thermally stable insensitive energetic materials have captivated significant attention from the global research community due to their potential impact. In this study, a series of symmetric and asymmetric nitromethyl-bridged triazole compounds were synthesized from pyrimidine moieties via a skeletal editing approach. Additionally, carbonyl-bridged compounds were synthesized in a single step by using acid-catalyzed Nef reactions from their nitromethyl precursors. Peripheral modifications of pyrimidine resulted in fused energetic moieties. All synthesized compounds were fully characterized by using infrared spectroscopy, high-resolution mass spectrometry, multinuclear magnetic resonance spectroscopy, elemental analysis, and differential scanning calorimetry. Single-crystal X-ray diffraction analysis confirmed the structures of compounds <b>4</b> and <b>10</b>. The newly synthesized moieties exhibit densities ranging from 1.75 to 1.86 g cm^-3, detonation velocities between 8044 and 8608 m s^-1, and detonation pressures between 23.10 and 30.31 GPa. Notably, compounds <b>9</b> and <b>10</b> demonstrate exceptional heat resistance, with decomposition temperatures of 315 and 335 °C, respectively. Computational studies, including density functional theory, quantum theory of atoms in molecules, noncovalent interactions, and electrostatic surface potential analysis, account for hydrogen-bonding and noncovalent interactions. This work highlights the potential of skeletal editing in the development of high-performing, thermally stable energetic materials.