Ultra heat-resistant hydrogen-bonded organic framework: Breaking the thermal stability limit of high-energy materials

The pursuit of heat-resistant energetic materials (HREMs) with thermal stability beyond 450 °C presents a significant challenge that has yet to be achieved. In this work, we develop an innovative electronic delocalization strategy to design and synthesize a planar dizwitterionic diamino-bistriazolotetrazine, designated as TYX-1. The unique structural feature of TYX-1, including a nitrogen-rich fused ring system, planar conformation, and dizwitterionic configuration, combined with its hydrogen-bonded organic framework (HOF) structure, confer exceptional thermal stability (The onset temperature is 428 °C, and the peak temperature is 473 °C), high density (1.84 g/cm 3 ), and remarkable detonation performance (detonation velocity: 8616 m/s). Furthermore, TYX-1 exhibits an impressive insensitivity (impact sensitivity > 40 J; friction sensitivity > 360 N), surpassing all previously reported HREMs. Theoretical calculations and single-crystal clearly indicate that the delocalized π electrons within the dizwitterionic bistriazolotetrazine rings and the HOF structure of TYX-1 are pivotal in ensuring its high thermal stability and high energy density. The discovery of TYX-1 marks a significant advancement in the field of HREMs and is anticipated to catalyze substantial progress in various high-temperature applications reliant on energetic materials. By integrating planar N -rich topology with zwitterionic polarization and π -delocalization, we break the traditional stability-energy trade-off. The dizwitterionic TYX-1 HOF achieves hierarchical stabilization via supramolecular π -stacking, electrostatic forces, and H -bonding, surpassing neutral/ionic systems. This 2D framework unites molecular bond density with macroscopic resilience, offering a paradigm for extreme-condition materials through cooperative molecular-supramolecular design. • Zwitterionic HOF achieves 473 °C stability & 8616 m s −1 detonation velocity simultaneously. • Nitrogen-rich fused-ring topology combines zwitterionic polarization with π -delocalization. • Multidimensional framework merges π -stacking, electrostatics and hydrogen bonds. • Charge-directed assembly enhances bond energy and structural integrity. • Molecular-supramolecular synergy co-optimizes conflicting energetic traits.