Structure Determination of [Au₁₈(SR)₁₄]

Abstract

Unravelling the atomic structures of small gold clusters is the key to understanding the origin of metallic bonds and the nucleation of clusters from organometallic precursors. Herein we report the X-ray crystal structure of a charge-neutral [Au18(SC6H11)14] cluster. This structure exhibits an unprecedented bi-octahedral (or hexagonal close packing) Au9 kernel protected by staple-like motifs including one tetramer, one dimer, and three monomers. Until the present, the [Au18(SC6H11)14] cluster is the smallest crystallographically characterized gold cluster protected by thiolates and provides important insight into the structural evolution with size. Theoretical calculations indicate charge transfer from surface to kernel for the HOMO-LUMO transition.

Polymorphism of Phosphine-Protected Gold Nanoclusters: Synthesis and Characterization of a New 22-Gold-Atom Cluster

“…Characterizations : NMR spectra were recorded on both a 400 and a 600 MHz Bruker Ultrashield spectrometer using CDCl 3 ) Ligand : 2-chloro-ethyl ether (2.5 mmol) was added to a 100 mL dry Schlenk fl ask. 20 mL tetrahydrofuran (THF) from a dry solvent dispensing system was then added to the Schlenk fl ask.…”

Bonding and properties of superatoms. Analogs to atoms and molecules and related concepts from superatomic clusters

“…The obtained structure exhibits a prolate Au 8 (bicapped octahedral) core protected by a combination of Au 2 (SR) 3 and Au(SR) 2 motifs. Later, Zhu and Jin group completely solved the Au 18 (SR) 14 structure using an X‐Ray diffraction approach, determining an Au 9 core which can be described as a tricapped octahedral core . Further analysis of the ligand effects on the vibrational, optical and chiroptical properties of thiolated Au 18 cluster has been provided by the same author, highlighting that bulkier ligands are able to interact between them if the required groups are introduced, for example, phenyl‐groups.…”

Chiral Gold Nanoclusters: Atomic Level Origins of Chirality

“…The second method is to directly fabricatec hiral nanostructures by templated deposition or growth, [44,45,53] and the third is to assemble achiral Au nanoparticles into chiral assemblies (e.g.,d iscrete oligomers of nanoparticleso rl arge-scale assemblies) with the aid of chiral templates. [65][66][67][68][69][70][71][72][73][74][75][76][77][78][79] More importantly,t he atomic structures of some nanoclusters have been unambiguously mapped out by using single-crystal X-ray crystallography, [64,65,[80][81][82][83][84][85][86][87][88][89][90] and thust he structures have explicitly revealed the atomic-level origin of chirality in the nanoclusters. [1,2,7] Ar ange of atomically precise sizes of gold nanoclusters have recently become assessable, particularly the thiolate-protected ones (denoted Au n (SR) m ,i nw hich n represents the precise number of gold atoms and m is the precise number of surfacet hiolate ligands).…”