Abstract
Superstructures with nanoscale building blocks, when coupled with precise control of the constituent units, open opportunities in rationally designing and manufacturing desired functional materials. Yet, synthetic strategies for the large-scale production of superstructures are scarce. We report a scalable and generalized approach to synthesizing superstructures assembled from atomically precise Ce24O28(OH)8 and other rare-earth metal-oxide nanoclusters alongside a detailed description of the self-assembly mechanism. Combining operando small-angle X-ray scattering, ex situ molecular and structural characterizations, and molecular dynamics simulations indicates that a high-temperature ligand-switching mechanism, from oleate to benzoate, governs the formation of the nanocluster assembly. The chemical tuning of surface ligands controls superstructure disassembly and reassembly, and furthermore, enables the synthesis of multicomponent superstructures. This synthetic approach, and the accurate mechanistic understanding, are promising for the preparation of superstructures for use in electronics, plasmonics, magnetics and catalysis.
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Data availability
The data supporting the findings of the study are available in the paper and its Supplementary Information. Source data are provided with this paper. Crystallographic data for the structure reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition number CCDC 2157579. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.
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Acknowledgements
This work was supported by the US National Science Foundation (CBET-2004808) and the Sloan Research Fellowship. We acknowledge UVA’s Nanoscale Material Characterization Facility (NMCF) for use of the XPS and SCXRD acquired under NSF MRI award DMR-1626201 and CHE-20188780, respectively. G.J. acknowledges support from the US Department of Energy (DOE), Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) programme. The SCGSR programme is administered by the Oak Ridge Institute for Science and Education for the DOE under contract number DE‐SC0014664. This work benefited from the use of the SasView application, originally developed under NSF Award DMR-0520547. SasView also contains code developed with funding from the EU Horizon 2020 programme under the SINE2020 project grant number 654000. This research used resources of the Advanced Photon Source, a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, under contract number DE-AC02-06CH11357. D.W. acknowledges an Individual Fellowship funded by the Marie Skłodowska-Curie Actions (MSCA) in the Horizon 2020 programme (grant 894254 SuprAtom). S.B. acknowledges support from the European Research Council (grant number 815128-REALNANO). The electron microscopy work was performed in part at the Analytical Instrumentation Facility (AIF) at North Carolina State University, which is supported by the State of North Carolina and the National Science Foundation (award number ECCS-2025064). The AIF is a member of the North Carolina Research Triangle Nanotechnology Network (RTNN), a site in the National Nanotechnology Coordinated Infrastructure (NNCI). G.L. gratefully acknowledges funding support by US NSF (DMR-1752611) and the Dean’s Discovery Fund at Virginia Tech. S.D. acknowledges support from the US DOE, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. P. Bean at the University of Virginia is acknowledged for his SEM contributions measuring the HEASS. We thank T. B. Gunnoe (University of Virginia), J. Elena (University of Virginia), D. E. Jiang (University of California, Riverside) and C. B. Murray (University of Pennsylvania) for project discussions.
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S.Z. and G.J. conceived and designed the experiments. W.A.G. and M.Y.Y. designed and performed the computational simulations. G.J. and C.L. performed the synthesis and analysed experimental data with help from B.A. under the supervision of S.Z. and S.D. G.J. and D.A.D. collected and analysed the SCXRD data. S.W., W.G., D.W. and S.B. performed STEM measurements of the materials. F.A.P. performed SSNMR experiments. G.J. and C.L. performed operando SAXS with assistance from H.Z. and X.Z. F.M. and C.Z performed MALDI-TOF experiments. Z.X. and G.L. performed TGA experiments. G.J. measured the XPS and Raman spectra. G.J., M.Y.Y., W.A.G. and S.Z. wrote the manuscript. All authors discussed the results and commented on the manuscript.
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Nature Synthesis thanks Matteo Cargnello, Taeghwan Hyeon, Paul Raithby 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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Table of contents, Supplementary Figs. 1–17, Table 1 and references.
Supplementary Data 1
Crystal data from the SCXRD measurement: CCDC 2157579.
Source data
Source Data Fig. 2
Numerical data for SAXS temperature profile (CeOx), SAXS time profile (CeOx), SSNMR data.
Source Data Fig. 3
xyz positions for Fig. 3a,b and numerical data for Fig. 3c,d.
Source Data Fig. 4
Numerical data of Fig. 4a,b and xyz positions for Fig. 4c.
Source Data Fig. 5
Numerical data for SAXS time profile of LaOx.
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Johnson, G., Yang, M.Y., Liu, C. et al. Nanocluster superstructures assembled via surface ligand switching at high temperature. Nat. Synth 2, 828–837 (2023). https://doi.org/10.1038/s44160-023-00304-8
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DOI: https://doi.org/10.1038/s44160-023-00304-8
