Tunable on-Demand Explosives Derived from Isoreticular Metal–Organic Framework Nanocomposites

Energetic metal–organic frameworks (MOFs) and MOF/oxidizer composites both suffer from thermal and mechanical sensitivity. Here, we present a molecular-level design strategy that overcomes this limitation by using nonenergetic components to prepare MOF-based composite energetic materials with tunable on-demand sensitivity and energetic behavior. In this two-component approach, porous, fuel-rich MOFs serve as catalytic host frameworks that support melt-infiltration of an oxidizing salt, facilitating nanoscopic mixing of fuel (linker), catalyst (metal node), and oxidizer. Linker extension achieves isoreticular pore expansion, dictates oxidizer loading capacity, oxidizer/fuel ratio, and catalyst density. A linker designed to minimize steric bulk and incorporate high-energy functional groups establishes the linker as a tunable design feature for controlling energetic decomposition. Across a series of isoreticular MOF/oxidizer formulations, higher oxidizer/fuel ratios and lower relative metal densities lead to greater energy output and gas release while also improving thermal stability; this represents a rare synergy. This approach yields energetic nanocomposites that are insensitive to impact, friction, and electrostatic shock yet transition to thermally sensitive explosives only after heat is supplied beyond the oxidizer melting point, constituting a rational design strategy to produce safer and tunable explosives.