Lithium-Promoted Formation of M-2AZTO-Li (M = N 2 H 5 + or NH 3 OH + and AZTO = Anion of 1-Hydroxytetrazole-5-hydrazide)-Type "Quaternary" Complexes with Nitrogen-Rich Characteristics: Construction of Novel Insensitive Energetic Materials.

Lithium-based nitrogen-rich complexes are important research objects in the field of high-energy materials. However, the weak coordination abilities of lithium ions relative to those of other metal ions with greater atomic numbers have hindered their applications in the field of nitrogen-rich complexes. Herein, we successfully prepared novel lithium-based nitrogen-rich complexes ( N 2 H 5 -2AZTO-Li and NH 3 OH-2AZTO-Li ) by exploiting the structural properties of 1-hydroxytetrazolium-5-hydrazine ( HAZTO ). Both N 2 H 5 -2AZTO-Li and NH 3 OH-2AZTO-Li were found to exhibit physicochemical parameters (including the density, stability, and energetic properties) that were intermediate between those of the simple ionic compounds ( 3 and 4 ) and the complexes ( 5 ) that formed them, enabling a favorable balance between high energy, high stability, and environmental friendliness (for N 2 H 5 -2AZTO-Li : detonation velocity ( D ) = 9005 m s -1 , detonation pressure ( P ) = 35.5 GPa, decomposition temperature ( T dec ) = 238.1 °C, impact sensitivity (IS) = 24 J, friction sensitivity (FS) = 210 N, and detonation product (DP) (CO) < 2%; for NH 3 OH-2AZTO-Li : D = 9028 m s -1 , P = 35.7 GPa, T dec = 211.2 °C, IS = 20 J, FS = 180 N, and DP (CO) < 2%). This study transcends the conventional structural forms of nitrogen-rich complexes, opening new horizons for the design of novel insensitive energetic materials.