Molecular Matching Strategy-Driven Supramolecular Stabilization of Poly-nitrogen Compounds

Abstract Poly-nitrogen compounds exhibit energy densities far exceeding those of traditional energetic materials, yet their poor stability limits their synthesis and applications. This work proposes a molecular matching strategy that systematically screens insensitive energetic compounds that match in electronic structure and geometry with representative poly-nitrogen systems (N6, N8, and N10), utilizing hydrogen bonds, π–π stacking, and other multiple weak interactions to construct supramolecular composites for stabilization and decomposition modulation. Multiscale simulations systematically investigate electronic structures, weak interaction networks, and thermal decomposition behaviors, revealing the underlying stabilization mechanism. ADCH analysis shows that ligand introduction induces significant charge redistribution and delocalization within the poly-nitrogen framework, with enhanced π-electron delocalization in bridging regions, corroborated by LOL-π and bond order analyses. IGMH and AIM analyses confirm extensive van der Waals interactions alongside hydrogen bonds and π–π stacking, with SAPT decomposition identifying dispersion as the dominant driving force, maximized in TATB systems. Transition state calculations demonstrate significantly increased decomposition barriers in composites, with barrier enhancement correlating positively with dispersion strength rather than total interaction energy. AIMD further confirms that ligands provide dynamic buffering through extensive weak interaction networks under thermal excitation, substantially delaying decomposition. Detonation performance indicates that these systems still exhibit excellent energy output levels. Benefiting from its superior stability and extensive weak interaction networks, the TATB system is an ideal candidate for stabilizing poly-nitrogen frameworks. This highlights the considerable potential of the molecular matching strategy for enhancing the safety of poly-nitrogen compounds and provides valuable insights for the composite design of poly-nitrogen molecules.