AbstractSeveral 1‐(2′,4′,6′‐trinitrophenyl)dinitrobenzimidazoles (1‐picryldinitrobenzimidazoles) were synthesized as part of an ongoing study of heterocyclic nitro compounds as energetic materials and their structure–property relationships. The 1‐picryl‐4,6‐dinitrobenzimidazoles and their 1‐methyl analogs were examined by several NMR techniques in order to confirm their structures, and assignment strategies are discussed. Nuclear Overhauser enhancement (NOE) difference spectroscopy and1H/13C correlation experiments were used to make definitive assignments of the1H and13C NMR spectra. It was found that both solvent and temperature had significant effects on the chemical shifts of the benzimidazole protons. This was especially true for the