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Atomically precise semiconductor clusters of rare-earth tellurides

Nature Synthesis (2024)Cite this article

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Abstract

Atomically precise clusters are important for understanding structure–property relationships of bulk materials. Here we report clusters of the general formula [K(2,2,2-cryptand)]2[(μ5-Cp*RE)6(μ6-κ3:κ3:κ3-Te3)(μ-κ2:κ2-Te2)(μ3-η2:κ:κ1-Te2)(μ3-Te)3] (Cp*, pentamethylcyclopentadienyl; RE = Y, Gd, Tb, Ho, Er). They are potential precursors to rare-earth tellurides, a class of topical quantum materials with interesting thermoelectric, magnetic, semiconducting and charge density wave properties. Crystallographic analyses reveal a common trigonal antiprismatic core of RE6Te10 with six RE atoms supported by three different types of tellurido ligands, namely Te2–, Te22– dianions, and a previously unknown tri-tellurido ligand Te34–, upon which the six RE atoms are hinged into a pseudo-D3d arrangement. Density functional theory studies reveal that the linear hypervalent Te34– ion has the electronic structure characteristics of a three-centre, four-electron bond. Studies by ultraviolet–visible–near infrared spectroscopy and theoretical analyses suggest that these clusters are semiconductors with comparable band gaps to those of monocrystalline silicon and gallium arsenide.

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Fig. 1: Core motifs of rare-earth telluride clusters.
Fig. 2: Ball-and-stick depiction of the crystal structure in Y6Te10.
Fig. 3: AdNDP analyses of the Te–Te bonds in Y6Te10.
Fig. 4: Chemical bonding analysis of Y6Te10 cluster.
Fig. 5: Electron localization analysis of Y6Te10 cluster.
Fig. 6: Evolution of the (F(R)hν)2 versus hν curves as a function of composition for RE6Te10 at room temperature.

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Data availability

Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2265362 (Y6Te10), 2265363 (Gd6Te10), 2265364 (Tb6Te10), 2265366 (Ho6Te10) and 2265367 (Er6Te10). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. The experimental data and the characterization data are available in the Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (92261203, 22101116, 21971106 and 22033005), the Key Laboratory of Rare-Earth Chemistry of Guangdong Higher Education Institutes (2022KSYS006), the Stable Support Plan Programme of Shenzhen Natural Science Fund (20200925161141006), the Shenzhen Fundamental Research Programme (JCYJ20220530115001002 and JCYJ20220818100417037), the National Key R&D Project (2022YFA1503900 and 2022YFA1503000) and the Guangdong Provincial Key Laboratory of Catalysis (2020B121201002). Computational resources are provided by the Center for Computational Science and Engineering and the CHEM high-performance supercomputer cluster at SUSTech. We thank X.-Y. Chang for assistance with single-crystal X-ray diffraction studies and discussion. We also thank Z. Quan, L. Mao, Z. Luo and Y. Liu for assistance with the solid-state UV-Vis-NIR characterization and discussion.

Author information

Author notes

  1. These authors contributed equally: You-Song Ding, Xue-Lian Jiang.

Authors and Affiliations

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

    You-Song Ding, Xue-Lian Jiang, Lei Li, Cong-Qiao Xu, Jun Li & Zhiping Zheng

  2. Key Laboratory of Rare-Earth Chemistry of Guangdong Higher Education Institutes, Southern University of Science and Technology, Shenzhen, China

    You-Song Ding, Xue-Lian Jiang, Lei Li, Cong-Qiao Xu, Jun Li & Zhiping Zheng

  3. Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Tsinghua University, Beijing, China

    Jun Li

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Contributions

Y.-S.D. synthesized and characterized the compounds with the assistance of L.L.; Z.Z. designed the research project and directed the experiments. X.-L.J. performed the DFT computations under the guidance of C.-Q.X. and J.L. The writing of the paper was completed using contributions from all authors who have also approved the final version of the paper.

Corresponding authors

Correspondence to Jun Li or Zhiping Zheng.

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Nature Synthesis thanks the anonymous reviewers 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 Tables 1–9, Figs. 1–12, Discussion and References.

Supplementary Data 1

Crystallographic data of Y6Te10, CCDC 2265362.

Supplementary Data 2

Crystallographic data of Gd6Te10, CCDC 2265363.

Supplementary Data 3

Crystallographic data of Tb6Te10, CCDC 2265364.

Supplementary Data 4

Crystallographic data of Ho6Te10, CCDC 2265366.

Supplementary Data 5

Crystallographic data of Er6Te10, CCDC 2265367.

Source data

Source Data Fig. 5

EDA–NOCV results of Y6Te10.

Source Data Fig. 6

Data of solid-state UV-Vis-NIR.

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Ding, YS., Jiang, XL., Li, L. et al. Atomically precise semiconductor clusters of rare-earth tellurides. Nat. Synth (2024). https://doi.org/10.1038/s44160-024-00511-x

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