Stabilization of golden cages by encapsulation of a single transition metal atom

Abstract

Golden cage-doped nanoclusters have attracted great attention in the past decade due to their remarkable electronic, optical and catalytic properties. However, the structures of large golden cage doped with Mo and Tc are still not well known because of the challenges in global structural searches. Here, we report anionic and neutral golden cage doped with a transition metal atom MAu16 (M = Mo and Tc) using Saunders ‘Kick' stochastic automation search method associated with density-functional theory (DFT) calculation (SK-DFT). The geometric structures and electronic properties of the doped clusters, MAu16q (M = Mo and Tc; q = 0 and −1), are investigated by means of DFT theoretical calculations. Our calculations confirm that the 4d transition metals Mo and Tc can be stably encapsulated in the Au16− cage, forming three different configurations, i.e. endohedral cages, planar structures and exohedral derivatives. The ground-state structures of endohedral cages C2v Mo@Au16−-(a) and C1 Tc@Au16−-(b) exhibit a marked stability, as judged by their high binding energy per atom (greater than 2.46 eV), doping energy (0.29 eV) as well as a large HOMO–LUMO gap (greater than 0.40 eV). The predicted photoelectron spectra should aid in future experimental characterization of MAu16− (M = Mo and Tc).

{Nano‐gold, iron(III)‐1,3,5‐benzene tricarboxylate metal organic framework (MOF)} nano‐composite as precursor for laser ablation generation of gold‐iron AumFen+/− (m = 1–35, n = 1–5) clusters. Mass spectrometric study

“…The intensity of Au m Fe + is lower than that of Au m + up to m = 14. Gold clusters with m = 12 and higher might have cage‐like structures where the host atom (Fe in our case) situated in the gold cage has a stabilisation effect and probably, because of this, those clusters (signals corresponding to them) start to have higher intensities than the gold clusters themselves (Figure 4B) . This fact was observed for all Au m Fe + ( m >13) clusters.…”

Symmetry lowering by cage doping in spherical superatoms: Evaluation of electronic and optical properties of 18‐electron W@Au12Ptn (n = 0‐4) superatomic clusters from relativistic DFT calculations

“…Actually, the Au 12 Pt 4 polyhedron in which W is encapsulated in Pt 4 -a has the same structural feature than that found previously for the [Au 16 ] 4− anion [85][86][87][88] and related Au 16 clusters encapsulating various elements. [37,[89][90][91] It is composed of an Au 12 truncated tetrahedron, the four hexagonal faces of which being capped by the four Pt atoms which in fact are situated close to the centers of the faces.…”

Stabilizing heteroatom‐centered 16‐vertex group 11 tetrahedral architectures: Bonding and structural considerations toward versatile endohedral species

“…In this work, we focus on the search for closed shell 18‐ je and 20‐ je neutral T d species related to that of [Au 20 ]. Open‐shell systems and/or nontetrahedral structures have been investigated by others …”

“…Among the many group 11 superatoms known so far, the [Au 20 ] tetrahedral cluster [15] is very particular in the way it does not need to bear any ligand shell to be stabilized. Its structure of T d symmetry is a piece of fcc bulk metal, which alternatively can be described as made of three concentric shells of symmetry-equivalent metals (M 0 4 @M 00 12 @M 000 4 ).…”

“…Open-shell systems and/or nontetrahedral structures have been investigated by others. [20][21][22] 2 | COMPUTATIONAL DETAILS All density functional theory (DFT) calculations were carried out by using the Amsterdam Density Functional (ADF) program. [23,24] For the sake of homogeneity, the same level of calculation was used for all the computed models.…”