Crystal engineering of dinitropyrazine-based sodium E-MOFs: toward thermally robust and low-sensitivity energetic materials

The strategic development of thermally stable and low-sensitivity 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, <i>via</i> 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 (<i>T</i>_d = 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 for tuning energetic behaviour through crystal engineering and exploiting intermolecular interactions.