An [Au₁₃]⁵⁺ Approach to the Study of Gold Nanoclusters

Abstract

Recently, many examples of gold nanoclusters have been synthesized due to their exceptional spectroscopic properties and potential applications in nanotechnology. In this work we put forward an approach based on the icosahedral [Au] unit and summarize three possible extensions of the unit: wrapping, bonding, and vertex sharing. We show that the electronic structure of such clusters can be treated in a more localized manner and show how the approach could be applied to understand the structure and bonding of a large variety of gold nanoclusters.

Insight into the Geometric and Electronic Structures of Gold/Silver Superatomic Clusters Based on Icosahedron M13 Units and Their Alloys

“…Flat‐shape Au 60 could be viewed as a 2D array of icosahedral Au 13 . Furthermore, based on well‐characterized [Au 60 Se 2 (PPh 3 ) 10 (SePh) 15 ] + , Lin and co‐workers analyzed this nanocluster by counting it as multiple icosahedra (Figure B) . For Au 60 , they first considered it as five separated icosahedra and then considered the assembly of them by sharing the vertex atom.…”

“…As the number of icosahedral M 13 units increased, the metal core of assembled nanoclusters changed from 1D to 3D . Experimental and theoretical research into the geometric and electronic structures of superatomic nanoclusters based on M 13 units will facilitate the development of intra‐ and intermolecular assemblies …”

Coinage Metal Superatomic Cores: Insights into Their Intrinsic Stability and Optical Properties from Relativistic DFT Calculations

“…One of the most prominent and widely studied example is [Au 25 (SR) 18 ] À ,w hich displays ah igh stabilityo wing to its geometric and electronic peculiarities. [11,14,[38][39][40] Whereast he chemistry of gold superatoms is nowadaysv ery well documented, with characterized atom-precise species ranging up to more than one hundred atoms; [17,41] that of silver is so far developed to al esser extent. [5] The formally [Au 13 ] 5 + core exhibits an 8-je count denot-ing an 1S 2 1P 6 electronic configuration, accounting for its high stabilityo wing to the shell-closing electron count.…”

Theoretical investigations on the structure–property relationships of Au13and AuxM13−xnanoclusters

“…35 According to this model, all these Au 13 NCs are 8-electron clusters with 1S 2 , 1P 6 jellium orbitals (S, P and D orbitals in superatom correspond to the atomic s, p and d orbitals, respectively). The HOMOs of all these Au 13 NCs feature the characteristic of P orbital, 36,37 while the LUMOs of all these Au 13 NCs feature the D orbital characteristics (Fig. 3).…”

“…3). 37 The doping effect of the foreign (Ag, Cu, and Pd) atom(s) According to the recent experimental studies, different foreign metal (Ag, Cu, and Pd) atom(s) with the electronic structures similar to Au could be doped into the Au 13 21 To understand the doping preference for different metal atoms, we rst examined the relative energy of the Au x M 13Àx structures with the foreign atom doping at different site. The 13 possible doping sites on Au 13 were roughly categorized into six groups: the metal center atom, the shell atom coordinating with the phosphine ligand (adjacent to three Au-Cl bonds for shell-a and adjacent to two Au-Cl bonds for shell-b/c), and the shell atom connecting with chloride (adjacent to one Au-Cl bond for shelld, and adjacent to none Au-Cl bond for shell-e).…”