Single-crystal-to-single-crystal intercalation of a low-bandgap superatomic crystal

Abstract

The controlled introduction of impurities into the crystal lattice of solid-state compounds is a cornerstone of materials science. Intercalation, the insertion of guest atoms, ions or molecules between the atomic layers of a host structure, can produce novel electronic, magnetic and optical properties in many materials. Here we describe an intercalation compound in which the host [Co6Te8(PnPr3)6][C60]3, formed from the binary assembly of atomically precise molecular clusters, is a superatomic analogue of traditional layered atomic compounds. We find that tetracyanoethylene (TCNE) can be inserted into the superstructure through a single-crystal-to-single-crystal transformation. Using electronic absorption spectroscopy, electrical transport measurements and electronic structure calculations, we demonstrate that the intercalation is driven by the exchange of charge between the host [Co6Te8(PnPr3)6][C60]3 and the intercalant TCNE. These results show that intercalation is a powerful approach to manipulate the material properties of superatomic crystals.

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Figure 1: Superatomic intercalation.
Figure 2: Crystal structures of the layered material before and after intercalation.
Figure 3: Optical absorption spectra and PDOS of layered material before and after intercalation.
Figure 4: Electrical transport properties of [Co6Te8(PnPr3)6][C60]3[TCNE]x.

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Acknowledgements

We thank R. Hastie for her help in making the figures. Funding for this research was provided by the Center for Precision Assembly of Superstratic and Superatomic Solids, and the National Science Foundation (NSF) Materials Research Science and Engineering Centers (MRSEC) (Award no. DMR-1420634). The spectroscopy for this project was supported by the Air Force Office of Scientific Research (Award no. FA9550-14-1-0381). E.S.O'B., R.K. and J.C. are supported by the MRSEC. G.A.E. acknowledges support by the Semiconductor Research Cooperation–Nanoelectronics Research Initiative Hans J. Coufal Fellowship and the Columbia Optics and Quantum Electronics NSF Integrative Graduate Education and Research Traineeship (DGE-1069240). X-ray diffraction measurements were performed in the Shared Materials Characterization Laboratory at Columbia University. Use of the Shared Materials Characterization Laboratory was made possible by funding from Columbia University. We thank C. Nuckolls, M. Steigerwald, L. Brus and C. Dean for the use of their instruments and for useful discussions.

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Contributions

E.S.O'B. synthesized the materials and, together with D.W.P., conducted the SCXRD characterization. M.T.T. and T.L.A. conducted the optical measurements. J.C., A.J.M. and D.R.R. formulated and performed the theoretical calculations. R.L.K., G.A.E. and A.M. fabricated the electrical devices and performed the electrical transport and Seebeck coefficient measurements. M.V.P., N.P. and A.C.C. measured the Raman spectra. E.S.O'B. wrote the manuscript with the help of M.T.T., and J.C., X.R., I.K., A.C.C., A.J.M., D.R.R. and X.Z. edited the manuscript. All the authors discussed the data and commented on the manuscript.

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Correspondence to Xavier Roy.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 1553 kb)

Supplementary information

Crystallographic data for compound [Co6Te8(PnPr3)6][C60]3[Toluene]6 (CIF 6811 kb)

Supplementary information

Crystallographic data for desolvated compound [Co6Te8(PnPr3)6][C60]3 (CIF 2004 kb)

Supplementary information

Crystallographic data for compound [Co6Te8(PnPr3)6][C60]3[TCNE]2 (CIF 1762 kb)

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O'Brien, E., Trinh, M., Kann, R. et al. Single-crystal-to-single-crystal intercalation of a low-bandgap superatomic crystal. Nature Chem 9, 1170–1174 (2017). https://doi.org/10.1038/nchem.2844

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