Abstract
Control over intermolecular assembly is critical for constructing dense and thermally robust energetic materials. Such control is essential for developing next-generation energetic materials suitable for high-temperature and industrial applications. Now we demonstrate that tetrazine platforms enable dual lattice-engineering pathways through hydrogen-bond-directed assembly in protonated salts and coordination-driven organization in nitroamine potassium derivatives. Protonated systems form densely packed ionic frameworks stabilized by cooperative N–H⋯O/N hydrogen bonding and π–π stacking interactions, while potassium salts introduce metal-mediated bridging interactions that generate extended coordination architectures. These materials exhibit high densities (up to 1.93 g cm−3), excellent thermal stability (Td up to 299 °C), and moderate sensitivities, providing a favorable balance between performance and safety. These characteristics highlight their potential for practical deployment in high-temperature energetic systems, including propellants, explosives, and gas-generating materials.