Crystal Engineering of Dinitropyrazine-Based Sodium E-MOFs: Toward Thermally Robust and Low-Sensitivity Energetic Materials

Abstract

The strategic development of thermally stable and low-sensitive energetic materials is vital for next-generation defence and aerospace applications. Herein, we report the synthesis of novel three-dimensional energetic metal–organic frameworks (E-MOFs), NaNODP, NaNPO, and MDPO, via a straightforward synthetic approach. The E-MOFs were confirmed by SCXRD and thoroughly characterized using PXRD, NMR, IR, TGA-DSC, and elemental analysis (EA). NaNODP and NaNPO demonstrate good detonation performance (VOD: 8100–7960 m s-1; DP: 22.13-22.47 GPa), high thermal stability (Td = 291-271 °C), and mechanical insensitivity (IS: >40 J; FS: >360 N), rendering them promising candidates for heat-resistant explosive applications exceeding TNT and HNS and comparable to TATB. Hirshfeld surface and 2D fingerprint analyses underscore the dominance of H⋅⋅⋅O and H⋅⋅⋅N contacts, which play a pivotal role in enhancing thermal stability and reducing mechanical sensitivity. This work offers a molecular-level approach to tuning energetic behaviour through crystal engineering and exploiting intermolecular interactions.