Series of AzTO-Based Energetic Materials: Effect of Different π-π Stacking Modes on Their Thermal Stability and Sensitivity.

π-Stacking is common in materials, but different π-π stacking modes remarkably affect the properties and performances of materials. In particular, weak interactions, π-stacking and hydrogen bonding, often have a great impact on the stability and sensitivity of high-energetic compounds. Therefore, several of energetic materials based on 1,1'-dihydroxyazotetrazole (1) with a nearly flat structure, such as the salts of aminoguanidine (2), 1,3-diaminoguanidine (3), imidazole (4), pyrazole (5) and triaminoguanidine (6), and a cocrystal of 2-methylimidazole (7), were designed and synthesized. Based on single-crystal diffraction data, thermal decomposition behaviors, and the mechanical sensitivity test, the compounds of 4, 5, and 7 with face-to-face π-π stacking display outstanding thermal stability and insensitivity.