Selective Coordination Assembly of a Stable and Energetic Metal Organic Framework with Chlorate Anions

Abstract Property modulation is critical for high-performance energetic materials, where structural tunability of energetic metal−organic frameworks (EMOFs) provides a powerful solution. Herein, incorporating oxidative guests into EMOFs creates redox synergies to boost detonation and laser initiation performance, where a rigid nitrogen-rich fused tricyclic Ditetrazolo[1,5-a:1′,5′-c]pyrazine was adopted as energetic ligand. Exploiting the versatile coordination behavior of Ag+, preferential coordination between silver ions and oxygen atoms from ClO3− was established, enabling the precise anchoring of this oxidative guest into a dinuclear silver-based 2D [Ag2(DTP)(ClO3)2]n (EMOF-1). Single crystal X-ray diffraction (SCXRD) reveals that the ClO3− anions are chemically bound to the framework via strong coordination bonds, thereby intrinsically reinforcing the structural stability. Consequently, EMOF-1 exhibits a near-zero oxygen balance superior to conventional chlorate-based EMOFs, driving an exceptional balance of properties: a high thermal decomposition temperature (Td = 201 °C), desensitized mechanical sensitivity (IS = 5 J, FS = 64 N), and rapid laser initiation (t < 2 ms, E < 20 mJ). This synergistic optimization successfully decouples the intrinsic trade-off between energy output, structural stability, and initiation sensitivity. This structural regulation strategy opens a generalizable pathway for exploiting oxidative-guest functionalized EMOFs, offering critical insights for the rational design of next-generation laser-initiated energetic materials.