Self-Assembly of Nitrogen-Rich Heterocyclic Compounds with Oxidants for the Development of High-Energy Materials

The development of energetic materials with high energy and low sensitivity has attracted immense interests due to their widespread applications in aerospace technology and national defense. In this work, a promising self-assembly strategy was developed to prepare three high-energy materials (1–3) through the introduction of oxidant molecules into the crystal voids of the parent materials. The structures of these new materials were comprehensively examined by infrared spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffraction. In these materials, three unique layer structures with hcb, sql, and interrupted sql topologies were observed, which were formed by the fused-ring-based energetic components. Windows with hexagonal, square, and rectangular structures were observed within these layer structures, which were occupied by H2O2, NO3–, and ClO4–, respectively. Oxidant molecules interacted with parent molecules via hydrogen bonds to form crystal structures of these materials. Moreover, the energetic property of these materials was estimated by computing methods. The calculation results revealed that these self-assembly materials exhibit excellent energetic properties. The highest energetic performance was observed for compound 3. The detonation velocity, detonation pressure, and specific impulse values were up to 9339 m·s–1, 42.5 GPa, and 308 s, respectively, which were greater than those of HMX. Furthermore, these materials exhibited good sensitivity, which was closely related to their unique crystal structures. The high performance of these materials indicated that the self-assembly strategy should be a promising method for the development of novel energetic materials.