Decoding the crystal engineering of graphite-like energetic materials: From theoretical prediction to experimental verification

Energetic materials with a graphite-like crystal structure always demonstrate better energy-sensitivity balance than the common ones. However, the knowledge on how to design a graphite-like energetic material is still limited and a rational design procedure for graphite-like energetic materials is much desired. Here, a set of systematic methods for discovering new graphite-like energetic materials is presented. We analyzed the intermolecular self-assembled behavior of graphite-like energetic materials and proposed a combined method of coplanar configuration searching (CCS) and point-chain-plane progressive intermolecular assembly (pcp-PIA) to predict and screen new graphite-like energetic materials. Furthermore, with a self-established high-throughput design system, we rapidly focused on a potential graphite-like energetic molecule (namely, 2-azido-5-nitropyrimidine-4,6-diamine, DANAP) from 426 candidates and finally experimentally verified its graphite-like crystal structure. We believe that the method presented here will have potential applications in guiding the crystal engineering of graphite-like energetic materials, thereby accelerating the discovery of new energetic materials with promising properties.