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Aromaticity rules

Nature Chemistry volume 14, pages 585–590 (2022)Cite this article

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In 1931, Erich Hückel published a landmark paper — the seed of the now famous 4n + 2 rule for aromaticity in annulenes that bears his name. Electron counting has since been extended to other classes of compounds, resulting in a multitude of rules aiming to capture the concept of aromaticity and its impact in chemistry.

Aromaticity plays an important role in chemistry, despite the fact that it is a concept with a somewhat imprecise definition1,2,3. It is commonly accepted that aromatic compounds are particularly stable and unreactive, whereas antiaromatic compounds are known to be unstable and reactive. The presence of (anti)aromatic reactants, intermediates, transition states or products therefore has a great influence on reaction mechanisms4.

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Fig. 1: Aromaticity rules for annulenes.
Fig. 2: Extension of aromaticity rules to polycyclic aromatic hydrocarbons and 3D systems.
Fig. 3: Cylindrical aromaticity.
Fig. 4: Combining or connecting rules.

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Acknowledgements

The following organizations are thanked for financial support: the Ministerio de Ciencia e Innovación (MICINN, project number PID2020-113711GB-I00) and the Generalitat de Catalunya (project number 2017SGR0039). I am grateful to A. Artigas and K. Jorner for their careful reading and suggestions of improvement.

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  1. Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Girona, Catalonia, Spain

    Miquel Solà

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Correspondence to Miquel Solà.

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Solà, M. Aromaticity rules. Nat. Chem. 14, 585–590 (2022). https://doi.org/10.1038/s41557-022-00961-w

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