Ultra heat-resistant hydrogen-bonded organic framework: Breaking the thermal stability limit of high-energy materials
Bojun Tan, Jinkang Dou, Jing Zhang, Xiong Yang, Jia‐Tong Ren, Changwei Tang, Jian Su, Gen Zhang, Siwei Song, Qinghua Zhang, Binghui Duan, Hongchang Mo, Minghui Xu, Xianming Lu, Bozhou Wang, Ning Liu
Abstract
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.