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Aromaticity and through-space electronic coupling in [2]catenanes comprising two intertwined globally electron-delocalized octaphyrinoid rings

Nature Synthesis (2025)Cite this article

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Abstract

π-Conjugated molecules with non-trivial topologies, such as catenanes and molecular knots, offer aromaticity and through-space electronic and magnetic interactions absent in traditional planar π systems. However, their synthesis remains challenging, with previous examples showing only localized aromaticity in individual benzenoid rings. Here we report the synthesis of a [2]catenane comprising 2 intertwined octaphyrinoid rings, each with 34 globally delocalized π electrons, achieved using a passive metal-template strategy with 2,2′-dipyrromethene as the directing ligand. X-ray crystallographic analysis reveals a nearly orthogonal spatial arrangement of the rings in neutral catenane, stabilized by multiple [NH···N] and [S···N] close contacts. These rings exhibit global aromaticity with entangled magnetic shielding interactions. Upon four-electron oxidation, the system converts to a tetracation with two globally antiaromatic (32π) rings, in which through-space bonding interactions diminish the antiaromatic destabilization. Notably, counterions also affect the (anti)aromaticity of the tetracations in the single-crystal state, highlighting a dynamic interplay between molecular topology, electronic structure and external interactions.

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Fig. 1: Molecular design and synthesis.
Fig. 2: Electrochemical and optical properties.
Fig. 3: X-ray crystallographic structures.
Fig. 4: Theoretical calculations of 1-Zn, 1-Zn4+·(SbF6−)4, 1 and 14+·(SbCl6−)4 in the ground state.
Fig. 5: 1H NMR (500 MHz) spectra.

Data availability

The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2407480 (3), 2407481 (1), 2407482 (1-Zn), 2407483 (8), 2407485 (1-Zn4+·(SbF6−)4), 2407486 (1-Zn4+·(SbCl6−)4), 2407487 (OCT-1), 2407488 (14+·(SbCl6−)4), 2407489 ([OCT-2 + H]+·(SbF6−)), 2407490 (OCT-1+··(SbF6−)) and 2407491 (OCT-12+·(BF4−)(Cl−)). Copies of the data can be obtained free of charge via the Cambridge Crystallographic Data Center at https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

Y.N. acknowledges financial support from the National Natural Science Foundation of China (grant number 22375085), the Guangdong Provincial Key Laboratory of Catalysis (grant number 22201124), the Guangdong Provincial Key Laboratory of Sustainable Biomimetic Materials and Green Energy (grant number 2024B121201003) and the Innovation Commission of Shenzhen Municipality (grant number 20231116124346001). J.W. acknowledges financial support from a Singapore MOE Tier 2 grant (MOE-T2EP10222-0003), the MOE Tier 3 program (MOE-000755-00) and the A*STAR MTC IRG project (M22K2c0083). Z.Z. acknowledges financial support from the National Natural Science Foundation of China (grant numbers 52350058, 22375059 and 52525306). We thank X. Chang for his support with X-ray diffraction data collection. We also thank H. Xia and Z. Xie for helpful discussions.

Author information

Authors and Affiliations

  1. Department of Chemistry, Southern University of Science and Technology, Shenzhen, China

    Yuguang Sui, Jiahang Hao & Yong Ni

  2. School of Chemistry and Chemical Engineering, Southeast University, Nanjing, China

    Zipeng Wang

  3. State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China

    Jiahang Hao & Zebing Zeng

  4. Department of Chemistry, National University of Singapore, Singapore, Singapore

    Shaofei Wu, Longbin Ren & Jishan Wu

Authors
  1. Yuguang Sui
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  2. Zipeng Wang
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  6. Zebing Zeng
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Contributions

Z.Z., J.W. and Y.N. conceived of the idea and supervised the project. Y.N. and Y.S. synthesized the compounds and collected the spectral data. Y.N., Y.S., Z.W., L.R. and S.W. performed theoretical calculations and X-ray analysis. Y.N., Y.S. and J.H. performed the magnetic measurements and analysis. All authors participated in writing the paper.

Corresponding authors

Correspondence to Zebing Zeng, Jishan Wu or Yong Ni.

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Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Mercedes Alonso, Milan Gembicky and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Thomas West, in collaboration with the Nature Synthesis team.

Additional information

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Extended data

Extended Data Fig. 1 Representations of the conformation and π-electronic configuration of 8.

a, Crystallographic structures depicted as oak ridge thermal ellipsoid plots (ORTEP) at 30% probability, which clearly clarify the double-twisted figure-eight conformation of 8. b, Calculated LOL-π isosurface map (isovalue: 0.3), the pink and blue surfaces are interlocked in space, revealing a double-sided lemniscular topology for the π system of 8. c, Calculated AICD plots with the magnetic field aligned along the Z-axis (perpendicular to the paper, isovalue 0.02). d, Calculated EDDB isosurface (isovalue 0.02). The AICD and EDDB plots showed discontiguous electron circuit along the conjugated backbone, manifesting the nonaromatic character of 8.

Supplementary information

Supplementary Information

Experimental methods and Supplementary Figs. 1–92 and Tables 1–15.

Supplementary Video 1

GIMIC of 1-Zn.

Supplementary Video 2

GIMIC of 1.

Supplementary Video 3

GIMIC of 1-Zn⁴⁺.

Supplementary Video 4

GIMIC of 1⁴⁺.

Supplementary Data 1

Crystal data for 3, CCDC 2407480.

Supplementary Data 2

Crystal data for 8, CCDC 2407483.

Supplementary Data 3

Crystal data for 1-Zn, CCDC 2407482.

Supplementary Data 4

Crystal data for 1, CCDC 2407481.

Supplementary Data 5

Crystal data for 1-Zn4+·(SbF6−)4, CCDC 2407485.

Supplementary Data 6

Crystal data for 1-Zn4+·(SbCl6−)4, CCDC 2407486.

Supplementary Data 7

Crystal data for OCT-1, CCDC 2407487.

Supplementary Data 8

Crystal data for 14+·(SbCl6−)4, CCDC 2407488.

Supplementary Data 9

Crystal data for [OCT-2 + H]+·(SbF6−), CCDC 2407489.

Supplementary Data 10

Crystal data for OCT-1+··(SbF6−), CCDC 2407490.

Supplementary Data 11

Crystal data for OCT-12+·(BF4−)(Cl−), CCDC 2407491.

Source data

Source Data Fig. 1

Statistical source data.

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Sui, Y., Wang, Z., Hao, J. et al. Aromaticity and through-space electronic coupling in [2]catenanes comprising two intertwined globally electron-delocalized octaphyrinoid rings. Nat. Synth (2025). https://doi.org/10.1038/s44160-025-00918-0

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