Development and Evolution of Energetic Cocrystals.

In spite of the importance of energetic materials to a broad range of military (munitions, missiles) and civilian (mining, space exploration) technologies, the introduction of new chemical entities in the field occurs at a very slow pace. This situation is understandable considering the stringent requirements for cost and safety that must be met for new chemical entities to be fielded. If existing manufacturing infrastructure could be leveraged, then this would offer a fundamental shift in the discovery paradigm. Cocrystallization is an approach poised to realize this goal because it can use existing materials and make new chemical compositions through the assembly of multiple unique components in the solid state. This account describes early proof-of-principle studies with widely used energetics in the field, including 2,4,6-trinitrotoluene (TNT) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), forming cocrystals with nonenergetic coformers that alter key properties such as density, sensitivity, and morphology. The evolution of these studies to produce cocrystals between two energetic components is detailed, including those exploiting new intermolecular interaction motifs that drive assembly such as halogen bonding. Implications of cocrystallization for performance, sensitivity to external stimuli, and manufacturability are explored at each stage. The derivation of many of these cocrystals from energetic materials in common use satisfies the goal of using materials already demonstrated to be cost-effective at scale and with well-understood safety profiles. The account concludes with a discussion of cocrystallizing molecules having excess of oxidizing power with those that are oxygen-deficient to push the limits of explosive performance to unprecedented levels. The purposeful production of an arbitrary combination of two solid components into a cocrystal is far from certain, but the studies described motivate the continued exploration of novel materials and the development of predictive models for identifying crystallization partners. When such cocrystals form, many of their most important properties cannot be predicted, pointing to another challenge for the purposeful development of energetic materials based on cocrystallization.