Diversifying energetic architectures via pyrimidine skeletal editing: From a common precursor to tunable performance

We report a pyrimidine skeletal editing strategy that divergently constructs two structurally distinct energetic materials from a common monocyclic precursor. Starting from 4,6-dichloro-5-nitropyrimidine, a chain-linked energetic material (3) and a fused-ring energetic material (5) were selectively synthesized via a simple two-step route, along with their ionic salts (3–1, 3–2, 5–1, 5–2). Single-crystal X-ray diffraction analysis not only confirmed their molecular structures but, more importantly, revealed their fundamentally divergent spatial architectures—a caged framework versus a planar fused-ring system—providing an ideal platform to study structure-property relationships. All synthesized compounds exhibit outstanding detonation performance (detonation velocity: 8129–9163 m·s-1; detonation pressure: 23.39–31.16 GPa) and thermal stability, while maintaining remarkably low mechanical sensitivity (IS > 10 J, FS > 360 N). These superior properties are attributed to their high nitrogen content, dense molecular packing, and extensive hydrogen-bonding networks. The developed synthetic route is both concise and efficient, offering a novel skeletal editing and reconstruction strategy for designing energetic materials with tunable performance.