Isomeric Cation Engineering Enables Composition Preserving Property Tuning in Energetic Salts

Abstract Cationic isomerism offers a means of tuning energetic assemblies while retaining molecular composition. Here, a constitutional isomer (C2) of the planar TATOT cation (C1) was used to transform a conventional 1:2 salt into a three-component 1:1:1 system. Replacing C1 with C2 preserves the overall composition while changing the molecular environment surrounding the energetic dianion. The resulting mixed cation salt exhibits changes in thermal stability, sensitivity, density, and energetic performance relative to the corresponding single cation system, demonstrating a composition preserving approach to tuning energetic salts.