3,3'-Dinitroamino-4,4'-azoxyfurazan and its derivatives: an assembly of diverse N-O building blocks for high-performance energetic materials.

On the basis of a design strategy that results in the assembly of diverse N-O building blocks leading to energetic materials, 3,3'-dinitroamino-4,4'-azoxyfurazan and its nitrogen-rich salts were obtained and fully characterized via spectral and elemental analyses. Oxone (potassium peroxomonosulfate) is an efficient oxidizing agent for introducing the azoxy N-oxide functionality into the furazan backbone, giving a straightforward and low-cost synthetic route. On the basis of heats of formation calculated with Gaussian 03 and combined with experimentally determined densities, energetic properties (detonation velocity, pressure and specific impulse) were obtained using the EXPLO v6.01 program. These new molecules exhibit high density, moderate to good thermal stability, acceptable impact and friction sensitivities, and excellent detonation properties, which suggest potential applications as energetic materials. Interestingly, 3,3'-dinitroamino-4,4'-azoxyfurazan (4) has the highest calculated crystal density of 2.02 g cm(-3) at 173 K (gas pycnometer measured density is 1.96 g cm(-3) at 298 K) for N-oxide energetic compounds yet reported. Another promising compound is the hydroxylammonium salt (6), which has four different kinds of N-O moieties and a detonation performance superior to those of 1,3,5,7-tetranitrotetraazacyclooctane (HMX), and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclododecane (CL-20). Furthermore, computational results, viz., NBO charges and ESP, also support the superior qualities of the newly prepared compounds and the design strategy.