Chemistry Seminar Series

Gold Superatoms and Superatomic Molecules Protected by Ligands

Speaker

Tatsuya Tsukuda

Institute

Department of Chemistry, School of Science, The University of Tokyo,Japan tsukuda@chem.s.u-tokyo.ac.jp

Time & Place

Wed, 02 Aug 2017 12:00:00 NZST in Rutherford Building, Level 5, Room 531

All are welcome

Abstract

Icosahedral Au13 clusters and deformed icosahedral Au11 clusters can be found as ubiquitous cores in ligand-protected Au clusters as evidenced by single-crystal X-ray diffraction (SCXRD) studies [1]. The high stability of these Au cores is explained in terms of the closure of geometric and electronic structures. The Au11/13 cores are fully protected by the ligands via Au-P, Au-Cl, Au-C, and Au-S bonds. A simple electron counting scheme predicts that the electronic structures of the Au11/13 cores are closed with the electron configuration of (1S)2(1P)6. In this regard, the Au13(8e) and Au11(8e) cores in the ligand-protected Au clusters can be viewed as spherical Au superatoms with rare-gas-like electron configuration. Synthesis of Au superatoms with non-rare-gas electron configuration is an interesting challenge toward the establishment of a periodic table of artificial elements on a nanoscale. Recent SCXRD studies demonstrated formation of a variety of dimeric structures of Au13 via different bonding modes: a vertex-sharing Au25(16e), face-sharing Au23(14e) and non-sharing Au26(16e). These examples suggest that a new class of artificial molecules (superatomic molecules) can be made using superatoms as building blocks [2].

The talk will cover the following topics on ligand-protected superatoms and superatomic molecules: (1) new spectroscopic characterization of Au superatoms [3–5]; (2) synthesis of Au-based superatoms with non-rare-gas electronic configurations [6–8]; (3) synthesis and characterization of Au superatomic molecules [9–12].

 

References

  1. T. Tsukuda and H. Häkkinen (eds.), “Protected Metal Clusters; From fundamentals to applications” (Elsevier, 2015).

  2. J. Nishigaki et al., Chem. Rec.14, 897–909 (2014).

  3. Y. Negishi et al., J. Phys. Chem. Lett.4, 3579–3583 (2013).

  4. S. Yamazoe et al., J. Phys. Chem. C 118, 25284–25290 (2014).

  5. S. Yamazoe et al., Nat. Commun. 7, 10414 (2016).

  6. S. Matsuo et al., Phys. Chem. Chem. Phys. 18, 4822–4827 (2016)

  7. S. Takano, T. Tsukuda, J. Phys. Chem. Lett. 7, 4509–4513 (2016)

  8. S. Takano et al., APL Mater. 5, 053402 (2017).

  9. J. Nishigaki et al., Chem. Commun. 50, 839–841 (2014).

  10. R. Takahata, et al., J. Am. Chem. Soc. 136, 8489–8491 (2014).

  11. S. Takano et al., J. Am. Chem. Soc.137, 7027–7030 (2015).

  12. S. Matsuo et al., ChemElectroChem 3, 1206–1211 (2016).