Hypergolic Copper Cluster‐Based Covalent Organic Frameworks

ABSTRACT Rational design of hypergolic materials that integrate rapid ignition with high energy density is of great significance for advancing propulsion technologies. Herein, we achieve synergistic enhancement in hypergolic performance by incorporating catalytic centers and energy units into a single covalent organic framework (COF) constructed from metal‐cluster nodes and carborane building blocks. A trinuclear copper cluster serves simultaneously as a structural building unit and a catalytic center, directing the formation of the reticular framework while activating an otherwise inert carborane‐based linker. The resulting COF inherits the hypergolic character of the copper clusters, exhibiting an ignition delay time of 40 ms with high‐test peroxide as the oxidizer, while the carborane cages impart a high energy density of 25.9 kJ g −1 . Theoretical simulations confirm strong interfacial interactions and a low reaction energy barrier between COF and oxidizer, supporting the design concept of synergistic performance. This work establishes a rational design strategy for the precise construction of functionalized hypergolic framework materials.