Template Directed Strategy of Green Energetic Metal-Organic Frameworks for Enhancing Oxygen Balance and Near Infrared Laser Initiation

Abstract

Template-directed strategies attract increasing attention in preparing Metal-Organic Frameworks (MOFs) due to their efficiency and flexibility. Special energetic metal-organic frameworks (EMOFs) are among the most promising candidates for laser-responsive energetic materials, but their structure, physical and chemical properties, and environmental performance control remain limited. In this study, a template-guided approach assembles an Ag-ATRZ cationic metal-organic framework (CMOF), yielding [Ag(ATRZ)(DN)] n (CMOF-1), an excellent lead-free and halogen-free laser-initiated primary explosive prepared via an efficient, green, low-toxic, and atom-economical "one-pot" method. Recrystallization further yielded a product with needle-like crystal morphology. The 3D structure of CMOF-1 has been confirmed through single-crystal X-ray diffraction. Notably, CMOF-1 has excellent thermal stability, with a thermal decomposition temperature of 210 °C. Directed by the template guest anion [N(NO 2 ) 2 ] -(DN -), CMOF-1 exhibits high explosive heat (9.56 kJ g -1 ) and an oxygen balance closer to zero than other Ag-ATRZ CMOFs, facilitating more efficient deflagration-to-detonation transition (DDT) behavior. Moreover, CMOF-1 is initiable by near-infrared laser irradiation (808 nm and 980 nm) at low energy thresholds (E < 10 mJ) and short delay times (t < 1 ms), significantly outperforming conventional laser-initiated metal complexes. This work offers a novel strategy for developing high-performance green laser-responsive energetic materials.