Hydrogen‐Bonded Molecular Scaffold Locks Metastable Amorphous Energetic Materials for Synergistic Energy Release and Safety

ABSTRACT Amorphous materials exhibit a unique combination of properties surpassing crystalline materials due to their disordered structure, opening new dimensions for numerous frontier fields. This state is introduced into energetic materials systems, where the challenge lies not only in constructing stable energetic molecular disordered frameworks; it also faces the dual challenge of coordinated safety and reactivity. Herein, we propose a hydrogen bond‐driven molecular assembly strategy using 4,4′,5,5′‐tetranitro‐1H,1′H‐[2,2′‐biimidazole]‐1,1′‐diamine (DATNBI) and hexanitrohexaazaisowurtzitane (CL‐20) as model systems. By constructing a 3D hydrogen bond network as a “molecular lock,” the stable amorphous DATNBI/CL‐20 (AEM‐DC) was successfully synthesized. This hydrogen‐bond framework effectively constrains molecular motion, forming a kinetic barrier that inhibits crystallization and elevates the crystallization temperature to 101.6°C. The material maintains high reactivity while achieving reduced impact sensitivity (17.5 J) and friction sensitivity (112 N). The material exhibits a combustion duration one to three times shorter and peak pressure 1.5 times higher than crystalline DATNBI, demonstrating synergistically enhanced energy release performance to its crystalline analogues. This result confirms the potential of noncovalent molecular frameworks in stabilizing metastable functional materials, offering a promising strategy for advancing the performance of energetic materials.