More nitro groups accord benzenes with higher energy but lower chemical stability. Hexanitrobenzene (HNB) with a fully nitrated structure has stood as the energy peak of organic explosives since 1966, but it is very unstable and even decomposes in moist air. To increase the energy limit and strike a balance between energy and chemical stability, we propose an interval full-nitro-nitroamino cooperative strategy to present a new fully nitrated benzene, 1,3,5-trinitro-2,4,6-trinitroaminobenzene (TNTNB), which was synthesized using an acylation-activation-nitration method. TNTNB exhibits a high density ( d : 1.995 g cm −3 at 173 K, 1.964 g cm −3 at 298 K) and excellent heat of detonation ( Q : 7179 kJ kg −1 ), which significantly exceed those of HNB ( Q : 6993 kJ kg −1 ) and the state-of-the-art explosive CL-20 ( Q : 6534 kJ kg −1 ); thus, TNTNB represents the new energy peak for organic explosives. Compared to HNB, TNTNB also exhibits enhanced chemical stability in water, acids, and bases.

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All-carbon-nitrated azoles have the advantages of high density and good oxygen balance, but they are rarely suitable for explosives applications due to their fatal deficiencies, such as poor thermal stability, sensitivity, and deliquescence. Cocrystallization technology provides a feasible idea to revive all-carbon-nitrated azoles in the presence of flexible structure designability and performance adjustability. In this study, three attractive energetic cocrystals 1−3 were synthesized with conjugate structure triimidazo[1,2-a:1′,2′-c:1″,2″-e][1,3,5]triazine (TT) and another all-carbon-nitrated azole [5-nitrotetrazole (HNT), 3,5-dinitro-1,2,4triazole (HDNT), and 3,4,5-trinitropyrazole (TNP)], respectively. All the cocrystals 1−3 existed stably and safely under natural conditions and exhibited better thermal stability, frictional sensitivity (FS), and impact sensitivity (IS) than pure HNT, HDNT, and TNP. Therein, two melting points (T m ) of 2 were 61.9 and 95.5 °C higher than that of HDNT, and its decomposition temperature (T d ) was 81.2 °C higher than that of HDNT. The mechanical sensitivity of 1 (FS = 80 N and IS = 24 J) was significantly improved compared with the extremely sensitive HNT (FS < 5 N and IS < 1 J). Moreover, 3 exhibited excellent controllable detonation performances (1.703 g cm −3 , 6903 m s −1 , and 18.0 GPa), which was better than 2,4,6-trinitrotoluene. The single-crystal structure analysis and theoretical calculation analysis showed that the formation of three cocrystals primarily depended on N−H•••N, C−H••• N, and C−H•••O hydrogen bonds and NO 2 •••π interaction with a π−π stacking. The thermal stability and sensitivity of 1−3 were obviously better than that of pure energetics, which was attributed to the combination of these strong hydrogen bond interactions and weak NO 2 •••π and π-stacking interactions. Therefore, the cocrystallization technology provides a promising method to give these "dead" all-carbon-nitrated azoles a new life.

Density is an important property of energetic materials and is believed to increase with the addition of heavy trinitromethyl groups, as shown in previous literature. However, this study determined that...