Potassium-Ion-Directed Three-Dimensional Assembly of a Dense and Thermally Robust Nitrogen-Rich Tetrazine Framework.

Potassium-ion-directed assembly of nitrogen-rich heterocycles provides an effective approach to dense energetic salts in which coordination interactions regulate crystal packing and thermal behavior. Now we report mono- and dipotassium-based salts derived from a nitrogen-rich tetrazine framework. Single-crystal X-ray diffraction of dipotassium AJE-2 reveals extensive K-O and K-N coordination interactions that generate three-dimensional networks reinforced by complementary N─H⋯O and N─H⋯N interactions. AJE-2 exhibits a room-temperature density of 2.01 g cm-3, a decomposition onset of 257°C, and sensitivity toward mechanical stimuli. These findings highlight the importance of metal-ion-directed assembly in stabilizing nitrogen-rich frameworks and provide insight into the design of potassium-based energetic materials with potential relevance to primary energetics.