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

Samir Kenouche, Nassima Bachir, Wissam Bouchal, Jorge I. Martínez-Araya

Research output: Contribution to journalArticlepeer-review

Abstract

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 NO2 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 NO2 groups, the ESP value in the ring center decreases as the NO2 groups are more closely spaced. As expected, the central rings become less aromatic as NO2 groups are added. The MCI, PDI, PLR, NICSzz(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 NICSzz(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.

Original languageEnglish
Article number108728
JournalJournal of Molecular Graphics and Modelling
Volume129
Early online date14 Feb 2024
DOIs
Publication statusE-pub ahead of print - 14 Feb 2024

Keywords

  • Aromaticity indices
  • ESP analysis
  • Nitro energetic molecules
  • Resonance energy

ASJC Scopus subject areas

  • Spectroscopy
  • Physical and Theoretical Chemistry
  • Computer Graphics and Computer-Aided Design
  • Materials Chemistry

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