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Capturing aromatic Cr5 pentagons in large main-group molecular cages

Nature Synthesis volume 4, pages 471–478 (2025)Cite this article

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Abstract

Chromium chemistry is attractive to researchers due to its interesting structural arrangements and unusual Cr–Cr bonding interactions. However, the exploration of polymeric Crn (n > 3) clusters is challenging because of the difficulty in achieving precise matching between the metal cores and ligands. To the best of our knowledge, planar Crn configurations beyond the Cr3 triangle have not been identified. In this study, we successfully isolated and characterized a Cr5 cluster using the Zintl ion synthesis route. This cluster exists within the ternary anion [Cr5Sn2Sb20]4− and the nanoscale dimer fusion anion [(Cr5)2Sn6Sb30]6−. Furthermore, we elucidated the aromatic properties of the Cr5Sn2 subunits through theoretical computational analysis, this aromaticity substantially enhancing the intrinsic stability of these Cr5 cluster species.

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Fig. 1: Synthesis of multi-bonded dichromium and chromium cluster-containing species using different synthetic strategies.
Fig. 2: Molecular structures of [Cr5Sn2Sb20]4− and [(Cr5)2Sn6Sb30]6−.
Fig. 3: AdNDP bonding patterns in [Cr5Sn2Sb20]4− and [(Cr5)2Sn6Sb30]6−.
Fig. 4: Calculated ICSSs of [Cr5Sn2Sb20]4− and [(Cr5)2Sn6Sb30]6−.

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Data availability

Crystallographic data for the structures reported in this paper have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers CCDC 2212806 (1a), 2212807 (1b) and 2322476 (2) and are freely available via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the paper and its Supplementary Information.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant nos. 22425107, 92461303, 22371140 and 92161102 to Z.-M.S and grant no. 22402108 to W.-J.T.), the Natural Science Foundation of Tianjin City (grant no. 21JCZXJC00140), the China Postdoctoral Science Foundation under Grant Number 2024M761514 and 111 Project of China (MOE, B18030). A.M.-C. thanks ANID FONDECYT Regular 1221676 for financial support.

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Author notes

  1. These authors contributed equally: Wei-Xing Chen, Wen-Juan Tian.

Authors and Affiliations

  1. State Key Laboratory of Elemento-Organic Chemistry, Tianjin Key Lab of Rare Earth Materials and Applications, School of Material Science and Engineering, Nankai University, Tianjin, China

    Wei-Xing Chen & Zhong-Ming Sun

  2. Institute of Molecular Science, Shanxi University, Taiyuan, China

    Wen-Juan Tian & Jing-Jing Wang

  3. Department of Chemistry, University of Oxford, Oxford, UK

    Zi-Sheng Li

  4. Facultad de Ingeniería, Arquitectura y Diseño, Universidad San Sebastián, Santiago, Chile

    Alvaro Muñoz-Castro

  5. Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing, China

    Gernot Frenking

  6. Fachbereich Chemie, Philipps-Universität Marburg, Marburg, Germany

    Gernot Frenking

  7. Donostia International Physics Center (DIPC), Donostia, Spain

    Gernot Frenking

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Contributions

Z.-M.S. conceived the project and designed the experiments. W.-X.C. conducted the syntheses. W.-J.T., Z.-S.L., J.-J.W., A.M.-C. and G.F. performed the quantum chemical calculations and analysed the data. Z.-M.S., W.-X.C., W.-J.T. and A.M.-C. co-wrote the paper. All authors reviewed the paper.

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Correspondence to Zhong-Ming Sun.

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Nature Synthesis thanks Jorge Barroso and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary discussion, Figs. 1–24 and Tables 1–8.

Supplementary Data 1

Crystallographic data for complex 1a.

Supplementary Data 2

Crystallographic data for complex 1b.

Supplementary Data 3

Crystallographic data for complex 2.

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Chen, WX., Tian, WJ., Li, ZS. et al. Capturing aromatic Cr5 pentagons in large main-group molecular cages. Nat. Synth 4, 471–478 (2025). https://doi.org/10.1038/s44160-024-00711-5

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