Hydrogen Bond and π-π Stacking Interaction: Stabilization Mechanism of Two Metal Cyclo-N₅ ^--Containing Energetic...

In recent years, cyclo-N₅ ^- has attracted extensive attention because all-nitrogen high-energy-density materials (HEDMs) have been expected to reach a TNT equivalent of over 3.0. However, for cyclo-N₅ ^--containing HEDMs, the stabilization mechanism has remained enigmatic. In this study, two typical cyclo-N₅ ^--containing metal hydrates, [Na(H₂O)(N₅)]·2H₂O (Na-cyclo-N₅ ^-) and [Mg(H₂O)₆(N₅)₂]·4H₂O (Mg-cyclo-N₅ ^-), are selected to gain insights into the factors affecting their stability by the first-principles method. Both binding/lattice energy calculations and density of states analysis show that Mg-cyclo-N₅ ^- is more stable than Na-cyclo-N₅ ^-. Hydrogen bonding is the main stabilization mechanism for stabilizing crystals and cyclo-N₅ ^-. Two types of hydrogen bonds, O-H···O and O-H···N, are clarified, which construct a 3D hydrogen bond network in Mg-cyclo-N₅ ^- and an intralayer 2D hydrogen bond network in Na-cyclo-N₅ ^-. Moreover, nonuniform stress causes distortion of cyclo-N₅ ^-. Comparing the two samples, the distortion degree of cyclo-N₅ ^- is higher in Na-cyclo-N₅ ^-, which indicates that cyclo-N₅ ^- decomposition is easier. These findings will enhance the future prospects for the design and synthesis of cyclo-N₅ ^--containing HEDMs.