Coordination Polymerization of Metal Azides and Powerful Nitrogen-Rich Ligand toward Primary Explosives with Excellent Energetic Performances

Advancement in explosive systems toward miniaturization and enhanced safety has prompted the development of primary explosives with powerful detonation performance and relatively low sensitivities. Energetic coordination polymers (ECPs) as a new type of energetic materials have attracted wide attention. However, regulating, the energetic characters of ECPs and establishing the relationship between structure and energetic property remains great challenges. In this study, two isomorphic 2D pi-stacked solvent-free coordination polymers, [M(N-3)(2)(atrz)](n) (M = Co 1, Cd 2; atrz = 4,4'-azo-1,2,4-triazole), were hydrothermally prepared and structurally characterized by X-ray diffraction. The two compounds exhibit reliable stabilities, Primary explosives remarkable positive enthalpies of formation, and prominent heats of detonation. The enthalpy of formation of 1 is 4.21 kJ.g(-1), which is higher than those of all hitherto known primary explosives. Repulsive steric clashes between the sensitive azide ions in 1 and 2 influence the mechanical sensitivities deduced from the calculated noncovalent interaction domains. The two energetic pi-stacked ECPs 1 and 2 can serve as candidates for primary explosives with an approved level of safety.