TY - JOUR
T1 - Perchlorate-type energetic coordination compounds
T2 - A new strategy for breaking the energy-sensitivity trade-off of energetic materials
AU - Zhang, Chao
AU - Wang, Tingwei
AU - Li, Shaoqun
AU - Lu, Zujia
AU - Li, Cong
AU - Xu, Meiqi
AU - Yu, Qiyao
AU - Zhang, Jianguo
N1 - Publisher Copyright:
© 2025 China Ordnance Society. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY-NC-ND license. http://creativecommons.org/licenses/by-nc-nd/4.0/
PY - 2026/7
Y1 - 2026/7
N2 - 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 (ClO4−) 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 1H-pyrazole-4-carbohydrazide ligands modified with electron-donating groups (methyl, amino, hydroxy). Single-crystal structural analysis confirmed the successful realization of the target dual structure in [Ag(3-APZ-CA)(ClO4)2]n, Ag(3-APZ-CA)2(ClO4)3, Cu(3-APZ-CA)2(ClO4)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 ClO4− 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.
AB - 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 (ClO4−) 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 1H-pyrazole-4-carbohydrazide ligands modified with electron-donating groups (methyl, amino, hydroxy). Single-crystal structural analysis confirmed the successful realization of the target dual structure in [Ag(3-APZ-CA)(ClO4)2]n, Ag(3-APZ-CA)2(ClO4)3, Cu(3-APZ-CA)2(ClO4)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 ClO4− 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.
KW - Dual structure
KW - Energetic coordination compounds
KW - Energetic materials
KW - Laser-ignitable
UR - https://www.scopus.com/pages/publications/105027166413
U2 - 10.1016/j.dt.2025.12.020
DO - 10.1016/j.dt.2025.12.020
M3 - Article
AN - SCOPUS:105027166413
SN - 2096-3459
VL - 61
SP - 126
EP - 135
JO - Defence Technology
JF - Defence Technology
ER -