Constructing Energetic Ionic Frameworks of Tetrazole with Enhanced Performance through Isomerism

Ionic framework materials have attracted considerable attention in chemistry and materials science. However, their synthesis predominantly relies on the precise selection of ionic components, often requiring a trial-and-error approach. This limitation has significantly impeded the efficient development of such materials. In this study, we propose a robust isomerism strategy that enables the structural transformation from non-framework to framework architectures in ionic systems. F -NH 3 NH 2 and F -NH 3 OH, the newly developed ionic frameworks, exhibit substantially higher energy and stability than their non-framework isomers, N -NH 3 NH 2 and N -NH 3 OH. Remarkably, F -NH 3 OH achieves an exceptional detonation performance, with a velocity of 9442 m/s and a pressure of 38.4 GPa, and mechanical sensitivity, with a friction sensitivity of 120 N and an impact sensitivity of 7 J, rivaling the representative explosive HMX. Single-crystal X-ray diffraction analysis coupled with quantum chemical calculations reveal that the enhanced performance of these ionic framework materials originates from reinforced hydrogen-bonding networks enabled by their complete structural coverage. This work not only provides new insights into the construction of ionic frameworks but also deepens our understanding of how isomerization influences both structure and properties in material science at the molecular level.