Icosahedral gold cage clusters: M@Au12− (M=V, Nb, and Ta)

Abstract

We report the observation and characterization of a series of stable bimetallic 18-valence-electron clusters containing a highly symmetric 12-atom icosahedral Au cage with an encapsulated central heteroatom of Group VB transition metals, M@Au(12) (-) (M=V,Nb,Ta). Electronic and structural properties of these clusters were probed by anion photoelectron spectroscopy and theoretical calculations. Characteristics of the M@Au(12) (-) species include their remarkably high binding energies and relatively simple spectral features, which reflect their high symmetry and stability. The adiabatic electronic binding energies of M@Au(12) (-) were measured to be 3.70+/-0.03, 3.77+/-0.03, and 3.76+/-0.03 eV for M=V, Nb, and Ta, respectively. Comparison of density-functional calculations with experimental data established the highly symmetric icosahedral structures for the 18-electron cluster anions, which may be promising building blocks for cluster-assembled nanomaterials in the form of stoichiometric [M@Au(12) (-)]X(+) salts.

Controllable Assembly and Dehydrogenation Catalysis Activity of Urchinlike FeNi–Ru(tips) Amorphous Alloy Hierarchical Nanostructures

“…Its X-ray diffraction (XRD) pattern gives one broad halo at 458 in Figure 1D pattern (a), which corresponds to the standard face-centered cubic (fcc) structure with a random crystalline orientation. [17] After annealing at 773 K protected under argon, the phase transfers to a longrange chemically ordered fcc structure proved by XRD pattern (b) in Figure 1D. The XRD patterns of annealed products agree well with the fcc structure of FeNi (JCPDF no.…”

Evidence of hollow golden cages

“…We note that an icosahedral Au 12 cage with a central metal atom, M@Au 12 , has been predicted (19) and verified experimentally (20,23). Recently, a larger gold cage with a central atom (M@Au 14 ) has been predicted to be very stable (24).…”

Far‐Infrared Spectra of Yttrium‐Doped Gold Clusters AunY (n=1–9)

“…[22] For Au 16 species doped with Fe, Co, and Ni, detailed structural information was obtained with trapped-ion electron diffraction. [42] While all transitionmetal atoms are located inside the gold cage, [39][40][41][42][43] Si becomes part of it, but Ge and Sn are found on the surface of the cages. [22] Recently, this study has been extended to smaller anionic gold clusters containing 5-8 atoms and a Si, Ge, or Sn dopant atom.…”

“…Photoelectron spectroscopic studies have focused on the structures of anionic gold cages of 12 atoms doped with W and Mo, [39] V, Nb, and Ta, [40] anionic gold cages of 16 and 17 atoms doped with Cu, [41] and anionic cages of 16 gold atoms doped with Fe, Co, Ni, Ag, Zn, In, [42,43] and the maingroup elements Si, Ge, and Sn. [22] For Au 16 species doped with Fe, Co, and Ni, detailed structural information was obtained with trapped-ion electron diffraction.…”