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Programmable zigzag π-extension toward graphene-like molecules by the stacking of naphthalene blocks

Nature Synthesis volume 2, pages 838–847 (2023)Cite this article

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Abstract

Graphene-like molecules with a zigzag periphery are interesting because of their ability to host spin-polarized electronic edge states. Although progress has been made for the preparation of armchair-edged graphene-like molecules, a general synthetic strategy to zigzag type remains elusive. Herein, using acetylenedicarboxylates as the C2 insertion unit, we report a rapid and modular strategy to extend the π-conjugation in a zigzag fashion through a rhodium-catalysed sequential C2–H and C8–H activation-annulation of naphthalene ketones. Different from the reported C–H activation-annulation of aryl ketones with alkynes to form a five-membered indenol, fulvene or six-membered pyran oxonium, this [4 + 2] and [4 + 2] annulation sequence selectively undergoes C(sp3)–H cyclization to extend the naphthalene fragment. This programmable zigzag π-extension can be compared to the stacking of toy blocks, as the naphthalene fragments are added step by step along an alkyl chain, demonstrated by the synthesis of anthanthrene and subsequently peri-naphthacenonaphthacene. These products are easily transformed to electron transport materials and thermally activated delayed fluorescent materials.

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Fig. 1: The synthesis of armchair and zigzag-edged GLMs.
Fig. 2: Models for the C–H activation–annulation of aryl ketones with alkynes and optimization of the reaction conditions.
Fig. 3: Mechanism studies.
Fig. 4
Fig. 5: Synthetic applications.
Fig. 6: OTFT and TADF performances.

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Data availability

The data that support the findings of this study are available within the article and its Supplementary Information. The X-ray crystallographic coordinates for structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition number CCDC 2153377 (26), 2170028 (34), 2153378 (37) and 2153379 (52). These data can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk/data_request/cif. Source data are provided with this paper.

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Acknowledgements

We acknowledge support for this work from the National Natural Science Foundation of China (No. 22031007, J.You) and from the Office of China Postdoctoral Council, the International Postdoctoral Exchange Fellowship Program (No. 20190088, J.Yin).

Author information

Author notes

  1. These authors contributed equally: Jiangliang Yin, Jian Li.

Authors and Affiliations

  1. Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, People’s Republic of China

    Jiangliang Yin, Jian Li, Ya Wang, Yuming Zhang, Cheng Zhang, Zhengyang Bin, Yudong Yang & Jingsong You

  2. Chongqing Key Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, People’s Republic of China

    Haohua Chen & Yu Lan

  3. Department of Chemistry, University of Chicago, Chicago, IL, USA

    Daniel Pyle

  4. College of Chemistry, and Institute of Green Catalysis, Zhengzhou University, Zhengzhou, People’s Republic of China

    Yu Lan

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Contributions

J. Yin, J.L., Y.W. and Y.Z. performed the experiments and analysed the data. H.C. performed the DFT calculations. J. You designed and directed the project. Y.L. directed the DFT calculations. C.Z. directed the OTFT measurements. Z.B. directed the OLED measurements. J. Yin, J. You, J.L., H.C., D.P., Y.Y. and Y.L. wrote the manuscript. All authors contributed to discussions.

Corresponding authors

Correspondence to Yu Lan or Jingsong You.

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The authors declare no competing interests.

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Peer review information

Nature Synthesis thanks Haibo Ge, Andreas Hirsch and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Experimental Details, Sections I–XIV, Supplementary Tables 1–10 and Figs. 1–10.

Supplementary Data 1

Cif file for compound 26, CCDC 2153377.

Supplementary Data 2

Structure factors for compound 26, CCDC 2153377.

Supplementary Data 3

Cif file for compound 34, CCDC 2170028.

Supplementary Data 4

Structure factors for compound 34, CCDC 2170028.

Supplementary Data 5

Cif file for compound 37, CCDC 2153378.

Supplementary Data 6

Structure factors for compound 37, CCDC 2153378.

Supplementary Data 7

Cif file for compound 52, CCDC 2153379.

Supplementary Data 8

Structure factors for compound 52, CCDC 2153379.

Source data

Source Data Fig. 6

Source Data for Fig. 6b and 6d.

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Yin, J., Li, J., Chen, H. et al. Programmable zigzag π-extension toward graphene-like molecules by the stacking of naphthalene blocks. Nat. Synth 2, 838–847 (2023). https://doi.org/10.1038/s44160-023-00306-6

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