Metal-centred planar [15]annulenes

Binbin Xu, Dafa Chen, Kaidong Ruan, Ming Luo, Yuanting Cai, Jia Qiu, Wenhao Zhou, Bula Cao, Zhenyang Lin, Jonathan L. Sessler and Haiping Xia ()
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Binbin Xu: Southern University of Science and Technology
Dafa Chen: Southern University of Science and Technology
Kaidong Ruan: Southern University of Science and Technology
Ming Luo: Southern University of Science and Technology
Yuanting Cai: Southern University of Science and Technology
Jia Qiu: Southern University of Science and Technology
Wenhao Zhou: Southern University of Science and Technology
Bula Cao: Southern University of Science and Technology
Zhenyang Lin: The Hong Kong University of Science and Technology
Jonathan L. Sessler: The University of Texas at Austin
Haiping Xia: Southern University of Science and Technology

Nature, 2025, vol. 641, issue 8061, 106-111

Abstract: Abstract The discovery of ferrocene1 heralded the advent of modern organometallic chemistry. Characterized by the π-coordination of a metal by one or two planar annulene anions, ferrocenes and their analogues2–4 exemplify the archetype of out-of-plane annulene metal complexes. By contrast, the integration of metal within the annulene core to form in-plane annulene metal complexes featuring metal–carbon σ bonds has been obstructed not only by the synthetic difficulty and the non-planarity of annulenes with appropriate internal dimensions, but also by the difficulty of embedding the metal. These challenges have prevented the isolation of such in-plane annulene metal complexes. Here we report the preparation of three metal-centred planar [15]annulene frameworks. The most symmetrical fragment has D5h symmetry, with the metal centre shared by five identical five-membered rings. Density functional theory calculations demonstrate that metal d orbitals participate in conjugation with these five-membered rings, rendering all of them aromatic. The overall framework bears a loose structural and spectroscopic analogy to metallo-expanded porphyrins with multiple aza donors5, which thus provides a nexus between annulene chemistry and classic heteroatom-based coordination chemistry. The present systems display high stability and are easily functionalized. We thus suggest that metal-centred planar annulenes could emerge as promising building blocks for materials science.

Date: 2025
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DOI: 10.1038/s41586-025-08841-2

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