Intramolecular Assembly of Nitrobiazoles and an Ether Bridge: Toward Energetic Materials with Enhanced Energy and Safety.

Recently, the construction of novel fused-ring frameworks has become one of the most significant innovative approaches to access high-energy and thermostable energetic molecules. In this work, an ether bridge was utilized as a building block to construct energetic fused-ring skeletons for the first time. Two new [5,7,5]-tricyclic N-heterocycle-based backbones, ditriazole-1,3,6-oxadiazepine and pyrazole-triazole-1,3,6-oxadiazepine, were synthesized via a straightforward one-step synthetic route and the energetic performances of their derivatives were further evaluated. Containing an additional oxygen atom, high-density pyrazole-triazole backbone, and high crystal packing coefficient, the asymmetric molecule 2,10,11-trinitro-5,7-pyrazolo[1,5-][1,2,4]triazolo[5,1-][1,3,6]oxadiazepine () features a high crystal density of 1.825 g cm, much superior to those of the symmetrical analogues 2,10-dinitro-5,7-bis([1,2,4]triazolo)[1,5-:5',1'-][1,3,6]oxadiazepine (, = 1.758 g cm) and ( = 1.634 g cm). Meanwhile, the compounds and exhibit better thermal stability than the parent molecule ( = 251 °C), and their decomposition temperatures reach up to 303 and 294 °C, respectively. The remarkable overall performance of and strongly suggests them as appropriate candidates for heat-resistant explosives. Our study may give new insights into the close correlation of the structural properties of energetic fused-ring frameworks, and the universality of the asymmetric heterocycles combination strategy for designing advanced high-energy density materials (HEDMs) was emphasized again.