Aromaticity of six-membered nitro energetic compounds through molecular electrostatic potential, magnetic, electronic delocalization and reactivity-based indices
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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 zz(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 zz(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.
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Electron delocalization-based indices such as PDI and FLU are very sensitive to small variations in aromaticity.
“By studying the aromaticity of benzene, and mono-and polynitrobenzenes, Martínez-Araya with co-workers concluded that electron delocalization-based indices, such as PDI and FLU, are very sensitive to small variations in aromaticity [117].”
From Aromaticity and Antiaromaticity: How to Define Them (2025) · cites this paper as [117]
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- Authors
- Kenouche, S., Bachir, N., Bouchal, W., & Martínez-Araya, J. I.
- Affiliations
- University of Biskra (DZ)
- Venue
- Journal of Molecular Graphics and Modelling
- Publisher
- Elsevier BV
- Published
- 2024-06
- Volume
- 129
- Pages
- 108728
- ISSN
- 1093-3263 (ISSN-L)
- OpenAlex
- W4391825281
- Cited by
- 8
- References
- 79
- Citations by year
- 2026: 5 · 2025: 3
- FWCI
- 1.15
- Type
- journal article
- Language
- en
- Open access
- green
- repositorio.unab.cl
- Licence
- Locations
- Journal of Molecular Graphics and Modelling (publishedVersion)
- PubMed (publishedVersion)
- Repositorio Institucional Académico , Sistema de Bibliotecas Universidad Andrés Bello (UNAB) (Universidad Andrés Bello (UNAB)) (submittedVersion)
- Funders
- Agencia Nacional de Investigación y Desarrollo (1181504)
- Fondo Nacional de Desarrollo Científico y Tecnológico
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Synthesis and Properties of Aromatic Compounds
- Physical Sciences › Engineering › Mechanics of Materials › Energetic Materials and Combustion
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Advanced Chemical Physics Studies
- Keywords
- aromaticity, nitrobenzene, molecular electrostatic potential, π-hole, detonation sensitivity, electron delocalization
- MeSH terms
- Nitro Compounds, Nitrogen Dioxide, Static Electricity
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