Highly Selective Nitroamino Isomerization Guided by Proton Transport Dynamics: Full-Nitroamino Imidazole[4,5- d ]pyridazine Fused-Ring System.

Due to the advantage of the hydrogen bond system formed by nitroamino isomerization, by the calculations of hydrogen transfer in reported nitroamino explosives, the proton transport dynamics was first proposed to predict the nitroamino isomerization of energetic materials. With the calculated results of zero-point energy, the full-nitroamino fused energetic materials, 2,4-nitroamino-7-nitroimino-1,5-dihydro--imidazolo[4,5-]pyridazine () and 2,2',7,7'-tetranitromino-4,4'-azo-imidazolo[4,5-]pyridazine () were designed and successfully synthesized. The highly selective nitroamino isomerization of neutral compound is shown by X-ray diffraction. After the hydrogen transfer occurs, the intermolecular hydrogen bonds will greatly promote tight stacking, which enhances the density and thus a series of comprehensive properties of energetic materials. The theoretical calculations of zero-point energy explain perfectly the selectivity of hydrogen transfer between the nitroamino groups and the fused-ring skeleton for . The hydrogen atom transfer and selective isomerization of nitroamino energetic materials can be accurately predicted following proton transport dynamics, which provides computational bases and new ideas for the efficient design of fully nitroamino-based explosives.