A Reversible Nitroamino‐Based Switch Modulates Hydrogen‐Bonding Networks in Energetic Materials

Abstract The regulation of hydrogen‐bonding networks in molecular switches is critical for adaptive materials. However, most of the reported molecular switches are not capable of modulating hydrogen‐bonding networks in energetic materials, limiting high‐demand applications in explosives. In this work, the first high‐energy nitroamino‐based molecular switch is reported. It can control the complex hydrogen‐bonding systems of energetic materials by reversible cycling for property modulation. Through alkali‐acid stimulation, the nitroamino‐based switch undergoes dynamic transitions, which reconfigure H‐bond networks and separate twin crystals (in x‐ray verification). Supported by crystallography and theoretical modeling (e.g., the density of states), this switching mechanism modulates molecular planarity (Δ θ  > 60°) and optimizes the energy‐stability balance, obtaining a compound 6 ‐β with comprehensive properties comparable to classical explosives (e.g., RDX and HMX). By linking hydrogen‐bonding engineering and energetic materials science through the nitroamino‐based molecular switch, it facilitates superior energetic compounds that can be applied to defense equipment. In addition, our work establishes the nitroamino‐based switch as a generalized tool for molecular engineering, bridging dynamic hydrogen‐bonding control and self‐assembly materials design.