Impact of stereochemistry in 3D energetic materials science: a case based on peripheral editing of the 2,4,10-trioxaadamantane backbone

Stereoisomerism in energetic materials remains an underexplored area of research. Herein, two series of energetic stereoisomers, including four diastereomers of 2,4,10-trioxaadamantane-6,8,9-triyl trinitrate and three diastereomers of 9,9-dinitro-2,4,10-trioxaadamantane-6,8-diyl dinitrate, were synthesized based on the systematic alteration of their stereochemistry. The first cage-like energetic materials were generated that incorporate considerations of configurational isomerism. Notably, despite having the same molecular formulas and functional group positions, these stereoisomers exhibited some differences in density, stability, and detonation performance. These results suggest that rationally designed stereochemical editing can serve as an effective strategy for further development of high-performance energetic materials.