Fine-Tuning the Energetic Properties of Complexes through Ligand Modification

Abstract

The modification of the properties of energetic materials is significant not only for gaining insight into the correlation between the structure and properties but also for various applications. In this study, three bis-1,2,4-triazole derivatives containing different energetic groups such as NH2, NO2, and NHNO2 (5,5′-diamino-3,3′-bis-1,2,4-triazole (H2DABT), 5,5′-dinitro-3,3′-bis-1,2,4-triazole (H2DNBT) and 5,5′-dinitroimino-3,3′-bis-1,2,4-triazole (H2DNABT)) were chosen as ligands to tune the structures and energetic properties of their complexes. Single-crystal X-ray diffraction studies show that as the modifying groups on the bis-1,2,4-triazole ligand were varied from NH2 to NO2 and NHNO2, the densities of the resultant complexes gradually increased from 1.838 g cm–3 to 1.978 g cm–3 and 2.049 g cm–3 for Cu-based complexes, while for Zn-based complexes, the densities also showed a gradual increase from 1.818 g cm–3 to 2.044 g cm–3 and 2.056 g cm–3. Additionally, the thermal stabilities and sensitivities of these complexes were also determined, and their detonation properties were calculated by the modified Kamlet method. As a result, the energetic performances of these resultant complexes were successfully modulated. This work may provide an effective approach to modulate the energetic properties of complexes via introduction of different energetic groups into the ligands.

Energetic Cocrystal, Ionic Salt, and Coordination Polymer of a Perchlorate Free High Energy Density Oxidizer: Influence of pKa Modulation on Their Formation

“…Cocrystals 6 and 7 are insensitive to impact and friction, which are comparable to those of BTNMBT, while ionic salt 8 and ECP 9 are sensitive to impact. It is surprising that ionic salt 8 has a lower friction sensitivity (FS: 64 N) than that of ECP 9 (FS: 144 N), which is partially explained by their crystal packing and specific coordination environment. − …”

Nitrate anions embedded in rigid and cationic 3D energetic MOFs constructed by the chelating ligand towards insensitive energetic materials

“…1d and Table 2). 50,51 These energetic and sensitive nitrate anions are reinforced by abundant hydrogen bonds in local environments and protected by the 3D framework built by chelating ligands, which can greatly endow 1 with high stability and energy performance.…”

Development and Evolution of Energetic Cocrystals

“…These three 1:1 cocrystals of DNBT possessed crystallographic densities >1.75 g/cm 3 and were predicted to have good detonation properties (detonation velocities >7600 m/s and pressures >24 GPa) . These numerous multicomponent materials derived from DNBT serve as a case study for future cocrystal research. − …”