Intramolecular Multifunctionalization in a Fused N ‐Rich Scaffold Produces a Record‐Density CF 3 Energetic

ABSTRACT The trifluoromethyl (CF 3 ) group is attractive for increasing molecular density in high‐energy materials, but CF 3 ‐containing compounds typically suffer from modest detonation performance. Here we report a rational design and synthesis of a fused, nitrogen‐rich pyrazolo[5,1‐ c ][1,2,4]triazole scaffold that positions multiple energetic substituents — nitro, nitramino, trinitromethyl, and trifluoromethyl — in a compact intramolecular arrangement. Starting from 6‐amino‐7‐nitro‐3‐(trifluoromethyl)‐1 H ‐pyrazolo[5,1‐ c ][1,2,4]triazole ( 4 ), we prepar the target neutral high‐energy compound 6‐nitroamino‐7‐nitro‐3‐(trifluoromethyl)‐1 H ‐pyrazolo[5,1‐ c ][1,2,4]triazole ( 7 ) and, via targeted derivatization, an additional neutral compound ( 5 ) and a series of energetic ionic salts ( 4a – e and 5a – c ). The new compounds display densities of 1.81–1.99 g cm −3 , detonation velocities of 7312–9100 m s −1 , detonation pressures of 20.4–37.8 GPa, and decomposition temperatures of 130–354 °C. Notably, compound 7 reaches an exceptional density of ρ = 1.99 g cm −3 and shows D v = 9100 m s − 1 and P = 37.8 GPa ‒ exceeding reported neutral CF 3 ‐containing energetic compounds and surpassing RDX in detonation performance. These results highlight that the intramolecular arrangement of multiple energetic substituents within fused nitrogen‐rich frameworks is a viable strategy to achieve next‐generation, high‐energy‐density materials.