Abstract
K2DNNNAT, a three-dimensional potassium-based energetic metal-organic framework with positive oxygen balance (+18.06%), transforms a highly sensitive trinitromethyl energetic system into a thermally stable lead-free primary energetic material through multidimensional framework engineering. The resulting framework exhibits excellent thermal stability (Td= 268 °C) and high heat of detonation (5362 kJ kg) together with impact and friction sensitivities of 4 J and 60 N, respectively. Hirshfeld surface analysis reveals extensive K⋯O/O⋯K and nitro-rich intermolecular interactions that reinforce the three-dimensional coordination framework and contribute to enhanced thermal stability while moderating mechanical sensitivity. These findings demonstrate that multidimensional framework engineering combined with oxygen-balance regulation provides a promising strategy toward safer lead-free primary energetic materials.