Influence of nitroamino−nitroimino tautomerism: A useful theoretical supplement for nitroamino-based energetic materials

Nitroamino is an ideal high-energy group for constructing energetic compounds. The skeletal isomerization of nitroamino to nitroimino forms intramolecular HBs, thus resulting in better density, thermal stability and sensitivity. However, it is difficult to find nitroamino and nitroimino in the same environment for comparative analysis. A new compound, 5-Nitroamino-8-nitroimino-1,4-dihydropyrazino [2,3-d]pyridazine-2,3-dione (3), was designed and synthesized. The symmetric skeleton of pyrazino [2,3-d]pyridazine provides the same environment for both nitroamino and nitroimino groups. By using a variety of computational and graphical methods, a theoretical support for nitroamino-based energetic materials was produced by thoroughly examining the influence between nitroamino and nitroimino. The symmetrical planar skeleton creates the conditions for exploring both nitroamino and nitroimino. [Display omitted] •Designed a new energetic compound 3 with a novel symmetric skeleton pyrazino [2,3-d]pyridazine.•Explore a variety of computational methods as a theoretical supplement for nitroamino-based energetic materials.•The causes of nitroimino-nitroamino tautomerism and the resulting intra-HB effects are studied in depth.