Perchlorate-type energetic coordination compounds: A new strategy for breaking the energy-sensitivity trade-off of energetic materials

The field of energetic materials has long been constrained by a fundamental challenge known as the "energy-sensitivity trade-off." Although energetic coordination compounds (ECCs) offer a viable pathway to address this dilemma, achieving high energy output, low sensitivity, and superior laser ignition performance within a single-component material remains a formidable challenge. This study introduces a novel "perchlorate-type ECCs" design strategy, which integrates additional oxidative perchlorate anions (ClO 4 − ) into the coordination framework via hydrogen-bond-driven self-assembly to construct a unique dual structure of "perchlorate salt+coordination compound". Based on this approach, six novel Ag(I)/Cu(II)-based ECCs were successfully synthesized using 1 H -pyrazole-4-carbohydrazide ligands modified with electron-donating group (methyl, amino, hydroxy). Single-crystal structural analysis confirmed the successful realization of the target dual structure in [Ag(3-APZ-CA)(ClO 4 ) 2 ] n , Ag(3-APZ-CA) 2 (ClO 4 ) 3 , Cu(3-APZ-CA) 2 (ClO 4 ) 4 . The design exhibits synergistic effects: (1) enhancing energy output by increasing oxygen balance, leading to higher detonation velocity ( D > 7.4 km/s) and detonation pressure ( P > 30.2 GPa); (2) reducing sensitivity, as protonated ligands and extra ClO 4 − provide abundant hydrogen-bond donors and acceptors, forming an extended intermolecular interaction network that desensitizes the materials. Furthermore, the dual-structural ECCs exhibit ultralow ignition energy thresholds under 808 nm (e.g., ECC-5 requires only 12 mJ) and achieve rapid deflagration-to-detonation transition (DDT), ensuring reliable initiation to RDX. This work not only develops a series of high-performance perchlorate-type ECCs but, more importantly, firstly provides a systematic strategy to overcome the energy-sensitivity trade-off.