Aromaticity of six-membered nitro energetic compounds through molecular electrostatic potential, magnetic, electronic delocalization and reactivity-based indices.

The electron density depletion associated with π -hole at the ring center typical of energetic compounds was clearly revealed by the molecular electrostatic potential (ESP). In addition, the spatial arrangement of NO 2 groups appears to affect the ESP value in the ring center, and therefore sensitivity to detonation. Indeed, for monocyclic nitrobenzene compounds with the same number of NO 2 groups, the ESP value in the ring center decreases as the NO 2 groups are more closely spaced. As expected, the central rings become less aromatic as NO 2 groups are added. The MCI, PDI, PLR, NICS z z (1), FLU indices are all strongly correlated with the ESP values observed in the ring center of the set of nitrobenzenes. Aromaticity indices based on electron delocalization criteria appear to be very sensitive to small variations in aromaticity. Among magnetic-based indices, only NICS z z (1) is capable to predict small changes in aromaticity. The PLR index derived from conceptual DFT is quite relevant for predicting small variations in aromaticity. According to our results, the most suitable aromaticity index is not based on a single criterion, and that selecting it is more subtle. Therefore, it is important to combine information from several criteria to obtain a more complete description of the aromaticity of the studied compounds. [Display omitted] • Spatial arrangements of NO 2 groups affect the ESP value at the ring center. • ESP value at the ring center decreases as the NO 2 groups are closely spaced. • Central rings become less aromatic as NO 2 groups are added. • NICS z z (1) is capable of properly predicting small changes in aromaticity. • Delocalization-based indices are sensitive to slight changes in aromaticity. [ABSTRACT FROM AUTHOR]