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Superatomic solid solutions


In atomic solids, substitutional doping of atoms into the lattice of a material to form solid solutions is one of the most powerful approaches to modulating its properties and has led to the discovery of various metal alloys and semiconductors. Herein we have prepared solid solutions in hierarchical solids that are built from atomically precise clusters. Two geometrically similar metal chalcogenide clusters, Co6Se8(PEt3)6 and Cr6Te8(PEt3)6, were combined as random substitutional mixture, in three different ratios, in a crystal lattice together with fullerenes. This does not alter the underlying crystalline structure of the [cluster][C60]2 material, but it influences its electronic and magnetic properties. All three solid solutions showed increased electrical conductivities compared with either the Co- or Cr-based parent material, substantially so for two of the Co:Cr ratios (up to 100-fold), and lowered activation barriers for electron transport. We attribute this to the existence of additional energy states arising from the materials’ structural heterogeneity, which effectively narrow transport gaps.

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Fig. 1: A general principle for the design and construction of superatomic solid solutions.
Fig. 2: Structures and compositions of superatomic solid solutions.
Fig. 3: Electronic and magnetic properties of superatomic solid solutions.
Fig. 4: Spectroscopic and computational investigations of superatomic solid solutions.

Data availability

The authors declare that all data supporting the findings of this study (details of the synthesis and characterization, measurements of electric transport and electronic and magnetic properties, theoretical calculations) are available within the paper and its Supplementary information. Source Data for Fig. 2b,c, Fig. 3a,b,d and Fig. 4a are provided. Data for the Supplementary Figures are included as Supplementary Data. The atomic coordinates for the optimized structures used for electronic structure and dimer formation energy calculations are provided in the .xlsx file named Supplementary_Tables.xlsx, and the optimized structures from DFT calculation in cif format are contained in file named Source data are provided with this paper.


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C.N. thanks S. Buckler and D. Buckler for their generous support. Support for this research was provided by the Center for Precision Assembly of Superstratic and Superatomic Solids, an NSF MRSEC (award nos. DMR-2011738 and DMR-1420634) and the Air Force Office of Scientific Research (award no. FA9550-18-1-0020). Shared Materials Characterization Laboratory at Columbia University, maintained using funding from Columbia University for which we are grateful. J.C.R. is supported by the NDSEG fellowship programme. Raman spectroscopy measurements were supported by the Barnard College Department of Chemistry and Office of the Provost. Electrical conductivity measurements were supported by the Army Research Office grant no. ARO#71641-MS. Use of the National Synchrotron Light Source II, Brookhaven National Laboratory, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-SC0012704. The DFT calculations were undertaken with the assistance of resources and services from the National Computational Infrastructure (NCI), which is supported by the Australian Government, and the computational cluster Katana supported by Research Technology Services at UNSW Sydney.

Author information

Authors and Affiliations



J.Y. and C.N. conceived the idea and designed the research. J.Y., X.R., M.L.S. and C.N. guided the research. J.Y. developed the synthesis, performed material characterizations and superconducting quantum interference device measurements. J.C.R. performed the electrical conductance measurement. S.T. and S.J.L.B. performed PDF measurements and analysis. S.R.P. performed SEM imaging. A.C.H. and A.C.C. performed Raman measurements. M.L. and D.R.R. performed computational analysis. J.Y., F.W. and X.Z. performed spectroscopic measurements. E.A.D. and E.S.O’B. provided the two clusters. N.G. for helpful discussion. J.Y., M.L.S. and C.N. wrote the manuscript with contributions from all authors.

Corresponding authors

Correspondence to Jingjing Yang, Xavier Roy, Michael L. Steigerwald or Colin Nuckolls.

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Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Chemistry thanks Delia Millirons, and the other anonymous reviewers for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–23, Discussion and Tables 1–9.

Supplementary Table 1

Supplementary Tables 10–16: atomic coordinates for the optimized structures used for electronic structure and dimer formation energy calculations.

Supplementary Data 1

Source data for Supplementary Figs. 8, 16, 17, 18, 19 and 20.

Supplementary Data 2

Optimized structures from DFT calculation in cif format.

Source data

Source Data Fig. 2

Statistical Source Data for Fig. 2b,c.

Source Data Fig. 3

Statistical Source Data for Fig. 3a,b,d.

Source Data Fig. 4

Statistical Source Data for Fig. 4a.

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Yang, J., Russell, J.C., Tao, S. et al. Superatomic solid solutions. Nat. Chem. 13, 607–613 (2021).

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