A new family of high-nitrogen compounds, that is, polyazido- and polyamino-substituted N,N′-azo-1,2,4-triazoles, were synthesized in a safe and convenient manner and fully characterized. The structures of 3,3′,5,5′-tetra(azido)-4,4′-azo-1,2,4-triazole (15) and 3,3′,5,5′-tetra(amino)-4,4′-azo-1,2,4-triazole (23) were also confirmed by X-ray diffraction. Differential scanning calorimetry (DSC) was performed to determine their thermal stability. Their heats of formation and density, which were calculated by using Gaussian 03, were used to determine the detonation performances of the related compounds (EXPLO 5.05). The heats of formation of the polyazido compounds were also derived by using an additive method. Compound 15 has the highest heat of formation (6933 kJ kg⁻¹) reported so far for energetic compounds and a detonation performance that is comparable to that of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), while compound 23 has a decomposition temperature of up to 290 °C.

A family of 4,4′,6,6′-tetra(azido)azo-1,3,5-triazine-N-oxides was designed and investigated by theoretical method. The effects of the NO bond on the properties of TAAT-N-oxides, such as density, heat of formation, and detonation performance, were discussed. By comparison with the bond-dissociation energy of the weakest bond and the electrostatic potentials, the effects of the NO bond on the stability and impact sensitivity of organic azides were also discussed. The results show that the introduction of NO bonds at the appropriate positions increases the oxygen balance and density of the compounds, while it has little effect on the stability and impact sensitivity. Consequently, their introduction results in energetic compounds with improved detonation performances.