LAUSR

Exploring the design strategy of new energetic materials is crucial to promote the development of energetic materials. In this study, a method for designing polycyclic energetic materials is proposed by combining the azetidine structure with azobis-1,2,4-triazole or bi-1,2,4-triazole. A series of typical triazolyl polycyclic compounds were designed and synthesized by simple nucleophilic reaction, which included 5,5′-dichloro-3,3′-bis(3,3′-difluoroazetidine)-4,4′-azobis-1,2,4-triazole (1), 5,5′-dichloro-3,3′-bis(3,3′-difluoroazetidine)-4,4′-bi-1,2,4-triazole (2), 5,5′-dichloro-3-(N,N-dimethyl)-3′-(3,3′-difluoroazetidine)-4,4′-bi-1,2,4-triazole (3) 5,5′-dichloro-3,3′-bis(3,3′-dinitroazetidine)-4,4′-bi-1,2,4-triazole (4), 5,5′-dichloro-3-(N,N-dimethyl)-3′-(3,3′-dinitroazetidine)-4,4′-bi-1,2,4-triazole (5), and 5,5′-diazido-3,3′-bis(3,3′-difluoroazetidine)-4,4′-azo-1,2,4-triazole (6). These designed and synthesized polycyclic compounds (1, 2, 3) have high decomposition temperatures (>200 °C). The molecular van der Waals surface electrostatic potentials suggested the reactivity of compounds 1, 2, and 3 when attacked by nucleophiles. The natural bond orbital and Hirshfeld surface analysis proved the essential reason for the stability of these compounds in theory. The formula design example suggests that some triazolyl polycyclic compounds (4, 5, and 6) are potentially explosives, suggesting that this strategy is feasible for constructing the triazolyl polycyclic energetic compounds.