Regulation of Crystal Packing and Energetic Performance of TNT Derivatives by Bromine Substitution

Improving the energetic performance of established explosives through rational structural modification provides an alternative strategy for the development of entirely new energetic molecules. In this work, bromine substitution was employed to regulate the solid-state properties of TNT derivatives, and two compounds, 3-bromo-2,4,6-trinitrotoluene (3-BrTNT) and 3,5-dibromo-2,4,6-trinitrotoluene (3,5-BrTNT), were synthesized and characterized. Single-crystal X-ray diffraction revealed that different bromination patterns lead to distinct crystal structures and packing characteristics. Electrostatic potential analysis and Hirshfeld surface analysis further revealed that bromine substitution modifies molecular surface characteristics and intermolecular contact distributions within the crystals. Compared with 3-BrTNT, 3,5-BrTNT exhibits a higher crystal density of 2.312 g cm−3 and improved calculated detonation performance, with a detonation velocity of 7915 m s−1 and a detonation pressure of 31.86 GPa. Meanwhile, both brominated derivatives exhibit reduced impact sensitivity compared with TNT. These results demonstrate that the bromination pattern, rather than bromine incorporation alone, plays an important role in regulating crystal structures and energetic properties. This study provides insight into substitution-pattern-controlled crystal engineering as a strategy for optimizing TNT-based energetic materials.