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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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 the.zip file named CIFs_DFT_Optimized_Structures.zip. Source data are provided with this paper.
Corrigan, J. F., Fuhr, O. & Fenske, D. Metal chalcogenide clusters on the border between molecules and materials. Adv. Mater. 21, 1867–1871 (2009).
Tomalia, D. A. & Khanna, S. N. A systematic framework and nanoperiodic concept for unifying nanoscience: hard/soft nanoelements, superatoms, meta-atoms, new emerging properties, periodic property patterns, and predictive Mendeleev-like nanoperiodic tables. Chem. Rev. 116, 2705–2774 (2016).
Jena, P. & Sun, Q. Super atomic clusters: design rules and potential for building blocks of materials. Chem. Rev. 118, 5755–5870 (2018).
Ni, B., Shi, Y. & Wang, X. The sub-nanometer scale as a new focus in nanoscience. Adv. Mater. 30, 1802031 (2018).
Yan, J., Teo, B. K. & Zheng, N. Surface chemistry of atomically precise coinage–metal nanoclusters: from structural control to surface reactivity and catalysis. Acc. Chem. Res. 51, 3084–3093 (2018).
Doud, E. A. et al. Superatoms in materials science. Nat. Rev. Mater. 5, 371–387 (2020).
Li, J., Li, X., Zhai, H.-J. & Wang, L.-S. Au20: a tetrahedral cluster. Science 299, 864–867 (2003).
Desireddy, A. et al. Ultrastable silver nanoparticles. Nature 501, 399–402 (2013).
Khanna, S. N. & Jena, P. Assembling crystals from clusters. Phys. Rev. Lett. 69, 1664–1667 (1992).
Claridge, S. A. et al. Cluster-assembled materials. ACS Nano 3, 244–255 (2009).
Chakraborty, P., Nag, A., Chakraborty, A. & Pradeep, T. Approaching materials with atomic precision using supramolecular cluster assemblies. Acc. Chem. Res. 52, 2–11 (2019).
Haddon, R. C. et al. Conducting films of C60 and C70 by alkali-metal doping. Nature 350, 320–322 (1991).
Hebard, A. F. et al. Superconductivity at 18 K in potassium-doped C60. Nature 350, 600–601 (1991).
Olson, J. R., Topp, K. A. & Pohl, R. O. Specific heat and thermal conductivity of solid fullerenes. Science 259, 1145–1148 (1993).
Hou, J. G. et al. Topology of two-dimensional C60 domains. Nature 409, 304–305 (2001).
Wang, L. et al. Long-range ordered carbon clusters: a crystalline material with amorphous building blocks. Science 337, 825–828 (2012).
Zeng, C., Chen, Y., Kirschbaum, K., Lambright, K. J. & Jin, R. Emergence of hierarchical structural complexities in nanoparticles and their assembly. Science 354, 1580–1584 (2016).
Roy, X. et al. Nanoscale atoms in solid-state chemistry. Science 341, 157–160 (2013).
Ong, W. L. et al. Orientational order controls crystalline and amorphous thermal transport in superatomic crystals. Nat. Mater. 16, 83–88 (2017).
O’Brien, E. S. et al. Single-crystal-to-single-crystal intercalation of a low-bandgap superatomic crystal. Nat. Chem. 9, 1170–1174 (2017).
Roy, X. et al. Quantum soldering of individual quantum dots. Angew. Chem. Int. Ed. 51, 12473–12476 (2012).
Hessen, B., Siegrist, T., Palstra, T., Tanzler, S. M. & Steigerwald, M. L. Hexakis(triethylphosphine)octatelluridohexachromium and a molecule-based synthesis of chromium telluride, Cr3Te4. Inorg. Chem. 32, 5165–5169 (1993).
Wells, A. F. Structural Inorganic Chemistry 5th edn (Oxford Univ. Press, 1984).
Chupas, P. J. et al. Rapid-acquisition pair distribution function (RA-PDF) analysis. J. Appl. Crystallogr. 36, 1342–1347 (2003).
Vegard, L. Die konstitution der mischkristalle und die raumfüllung der atome. Z. Phys. 5, 17–26 (1921).
Denton, A. R. & Ashcroft, N. W. Vegard’s law. Phys. Rev. A 43, 3161–3164 (1991).
Streetman, B. G. & Banerjee, S. K. Solid State Electronic Devices: Global Edition. (Pearson education, 2016).
Walid, A. et al. Large area epitaxial germanane for electronic devices. 2D Mater. 2, 035012 (2015).
Prencipe, I., Dellasega, D., Zani, A., Rizzo, D. & Passoni, M. Energy dispersive x-ray spectroscopy for nanostructured thin film density evaluation. Sci. Technol. Adv. Mat. 16, 025007–025007 (2015).
Urbach, F. The long-wavelength edge of photographic sensitivity and electronic absorption of solids. Phys. Rev. 92, 1324–1326 (1953).
Kuzmany, H., Matus, M., Burger, B. & Winter, J. Raman Scattering in C60 fullerenes and fullerides. Adv. Mater. 6, 731–745 (1994).
Reed, C. A. & Bolskar, R. D. Discrete fulleride anions and fullerenium cations. Chem. Rev. 100, 1075–1120 (2000).
Plank, W. et al. Resonance Raman excitation and electronic structure of the single bonded dimers C60 and (C59N)2. Eur. Phys. J. B 17, 33–42 (2000).
Winter, J. & Kuzmany, H. Charge transfer in alkali-metal-doped polymeric fullerenes. Phys. Rev. B 54, 17486–17492 (1996).
Konarev, D. V. et al. Formation of single-bonded (C60–)2 and (C70–)2 dimers in crystalline ionic complexes of fullerenes. J. Am. Chem. Soc. 125, 10074–10083 (2003).
Konarev, D. V., Khasanov, S. S., Otsuka, A., Saito, G. & Lyubovskaya, R. N. Negatively charged π-(C60–)2 dimer with biradical state at room temperature. J. Am. Chem. Soc. 128, 9292–9293 (2006).
Stephens, P. W. et al. Polymeric fullerene chains in RbC60 and KC60. Nature 370, 636–639 (1994).
Giacelone, F. & Martin, N. Fullerene polymers: synthesis and properties. Chem. Rev. 106, 5136–5190 (2006).
Turkiewicz, A. et al. Assembling hierarchical cluster solids with atomic precision. J. Am. Chem. Soc. 136, 15873–15876 (2014).
Dubois, D., Kadish, K. M., Flanagan, S. & Wilson, L. J. Electrochemical detection of fulleronium and highly reduced fulleride (C605−) ions in solution. J. Am. Chem. Soc. 113, 7773–7774 (1991).
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.
The authors declare no competing interests.
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Supplementary Figs. 1–23, Discussion and Tables 1–9.
Supplementary Tables 10–16: atomic coordinates for the optimized structures used for electronic structure and dimer formation energy calculations.
Source data for Supplementary Figs. 8, 16, 17, 18, 19 and 20.
Optimized structures from DFT calculation in cif format.
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Yang, J., Russell, J.C., Tao, S. et al. Superatomic solid solutions. Nat. Chem. 13, 607–613 (2021). https://doi.org/10.1038/s41557-021-00680-8
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