Structural Tailoring of Triazole‐Based Hypergolic Metal–Organic Complexes for Enhanced Ignition Performance and Energetic Output

Most hypergolic metal‐organic complexes derived from imidazole suffer from low energy density and specific impulse. Herein, triazole‐based hypergolic complexes are structurally modified to boost ignition and energetic properties. Eight complexes with diverse coordination environments, metal cores, and ligand skeletons are fabricated using high‐enthalpy 1,2,4‐triazole ligands and dicyandiamide as a hypergolic initiator. Cu‐DMAT‐1 and Cu‐DMAT‐2 possess Cu 3 O cores, while Cu‐AT‐8 features a Cu 4 O 2 cluster; these unique metal cores govern the materials’ hypergolic activity. All samples deliver ultra‐short ignition delay times (IDT) down to 4 ms against white fuming nitric acid. Cu‐AT‐8 shows optimal comprehensive performance (IDT = 7 ms, I sp = 271.6 s, ρ = 1.891 g/cm 3 , E g = 27.3 kJ/g, IS > 40 J, T d = 161.9°C). The IDT value is positively correlated with the HOMO–LUMO gap and intermetallic distance. These complexes effectively catalyze ammonium perchlorate (AP) decomposition, and the Cu‐DMAT‐3/AP mixture achieves a low relative standard deviation of 4.66% for combustion delay. Formulations blending the cluster complex, AP, and Al reach a peak I sp of 282.8 s for Cu‐AT‐8; solid grains burn steadily in air with little residue. Their laser ignition delays (65–134 ms) match well with oxidant‐drop test results.