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Cited by 35Synthesis and Properties of Aromatic CompoundsAdvanced Chemical Physics StudiesGraph theory and applications

Aromaticity Reversal Induced by Vibrations in Cyclo[16]carbon

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Rončević, Igor, Leslie, Freddie J., Rossmannek, Max, Tavernelli, Ivano, Gross, Leo, Anderson, Harry L.·2023·Journal of the American Chemical Society
DOI 10.1021/jacs.3c10207PMC PMC10722511

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Abstract

Aromaticity is typically regarded as an in-trinsic property of a molecule. It is often correlated with electron delocalization, stability, and other properties. Small variations in the molecular geometry usually result in small changes in aromaticity, in line with Hammond’s postu-late: for example, introducing bond-length alternation in benzene and square cyclobutadiene gradually decreases the magnitude of their ring currents, making them less aromatic and less antiaromatic, respectively. A sign change in the ring current, corresponding to a reversal of aromaticity, typically requires a gross perturbation such as electronic excitation, addition or removal of two electrons, or a dramatic change in the molecular geometry. Here, we use multireference calculations to show how small changes in bond-length alternation induce a sudden reversal in the ring current of cyclo[16]carbon, C16. This reversal occurs when the two orthogonal π systems of C16 sustain opposing currents. These results are rationalized by a Hückel model which includes bond-length alternation combined with a minimal model accounting for orbital contributions to the ring current. Finally, we successfully describe the electron-ic structure of C16 with a divide-and-conquer approach suitable for execution on a quantum computer.

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  • C16 has two orthogonal π-electron systems which are diatropic and paratropic in T1 and S1 electronic states.

    “The explanation lies in the fact that C 16 has two orthogonal π-electron systems which are diatropic and paratropic in T 1 and S 1 electronic states.”

    From Aromaticity and Antiaromaticity: How to Define Them (2025) · cites this paper as [175]

    The Results and Discussion section (T1 State; page unavailable) says the out-of-plane π system produces a diatropic current while the in-plane system produces a paratropic current. The S1 State section reports mixed aromaticity, but says both π systems have a combination of transitions; it does not establish that one system is diatropic and the other paratropic in S1. (LLM, conf=0.84)

    Experimental — accuracy not yet measured

  • Molecular vibrations that control the change in bond lengths of T1 and S1 cyclo[16]carbon cause a sudden change in the nature of ring currents, where the bond length alternating D8h structure is diatropic, while the D16h structure with BLA = 0 is paratropic.

    “Rončević and co-workers used theoretical calculations to show that molecular vibrations that control the change in the bond lengths of T 1 and S 1 cyclo [16]carbon cause a sudden change in the nature of ring currents, where bond length alternating the D 8h structure is diatropic, while the D 16h structure with BLA = 0 is paratropic.”

    From Aromaticity and Antiaromaticity: How to Define Them (2025) · cites this paper as [175]

  • The Kekulé vibrations change the relative strength of the paratropic and diatropic currents, leading to the reversal of the nature of overall ring currents.

    “The Kekulé vibrations change the relative strength of the paratropic and diatropic currents leading to the reversal of the nature of overall ring currents [175].”

    From Aromaticity and Antiaromaticity: How to Define Them (2025) · cites this paper as [175]

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Cited by

Sorted by citations

Authors
Rončević, I., Leslie, F. J., Rossmannek, M., Tavernelli, I., Gross, L., & Anderson, H. L.
Affiliations
  • University of Oxford (GB)
  • IBM Research - Zurich (CH)
Corresponding author
Rončević, Igor
ORCID
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2023-12-01
Volume
145
Issue
49
Pages
26962-26972
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/jacs.3c10207
PMC
PMC10722511
OpenAlex
W4389235211
Cited by
35
References
10
Citations by year
2026: 10 · 2025: 12 · 2024: 11 · 2023: 2
FWCI
3.58
Type
journal article
Language
en
Open access
Licence
Locations
  • Journal of the American Chemical Society (publishedVersion, cc-by)
  • ChemRxiv (acceptedVersion, cc-by-nc-nd)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • Research Explorer (The University of Manchester) (publishedVersion, cc-by)
Funders
  • HORIZON EUROPE Marie Sklodowska-Curie Actions (101064401)
  • H2020 European Research Council (885606, 951519)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Synthesis and Properties of Aromatic Compounds
  • Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Advanced Chemical Physics Studies
  • Physical Sciences › Mathematics › Geometry and Topology › Graph theory and applications
Keywords
ring current, bond alternation, multireference calculations, Hückel method, quantum computing

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