A series of chiral Au13 nanoclusters were synthesized via the direct reduction of achiral dinuclear Au(I) halide complexes ligated by ortho-xylyl–linked bis-N-heterocyclic carbene (NHC) ligands. A broad range of functional...
Although the self-assembly of organic ligands on gold has been dominated by sulfur-based ligands for decades, a new ligand class, N-heterocyclic carbenes (NHCs), has appeared as an interesting alternative. However, fundamental questions surrounding self-assembly of this new ligand remain unanswered. Herein, we describe the effect of NHC structure, surface coverage, and substrate temperature on mobility, thermal stability, NHC surface geometry, and self-assembly. Analysis of NHC adsorption and self-assembly by scanning tunneling microscopy and density functional theory have revealed the importance of NHC-surface interactions and attractive NHC-NHC interactions on NHC monolayer structures. A remarkable way these interactions manifest is the need for a threshold NHC surface coverage to produce upright, adatom-mediated adsorption motifs with low surface diffusion. NHC wingtip structure is also critical, with primary substituents leading to the formation of flat-lying NHC2Au complexes, which have high mobility when isolated, but self-assemble into stable ordered lattices at higher surface concentrations. These and other studies of NHC surface chemistry will be crucial for the success of these next-generation monolayers.
Herein, we describe
the synthesis of a toroidal Au
10
cluster stabilized by
N
-heterocyclic carbene and
halide ligands
via
reduction of the corresponding
NHC–Au–X complexes (X = Cl, Br, I). The significant
effect of the halide ligands on the formation, stability, and further
conversions of these clusters is presented. While solutions of the
chloride derivatives of Au
10
show no change even upon heating,
the bromide derivative readily undergoes conversion to form a biicosahedral
Au
25
cluster at room temperature. For the iodide derivative,
the formation of a significant amount of Au
25
was observed
even upon the reduction of NHC–Au–I. The isolated bromide
derivative of the Au
25
cluster displays a relatively high
(
ca
. 15%) photoluminescence quantum yield, attributed
to the high rigidity of the cluster, which is enforced by multiple
CH−π interactions within the molecular structure. Density
functional theory computations are used to characterize the electronic
structure and optical absorption of the Au
10
cluster.
13
C-Labeling is employed to assist with characterization of
the products and to observe their conversions by NMR spectroscopy.
Benzimidazolium hydrogen carbonate salts have been shown to act as N‐heterocyclic carbene precursors, which can remove oxide from copper oxide surfaces and functionalize the resulting metallic surfaces in a single pot. Both the surfaces and the etching products were fully characterized by spectroscopic methods. Analysis of surfaces before and after NHC treatment by X‐ray photoelectron spectroscopy demonstrates the complete removal of copper(II) oxide. By using 13C‐labelling, we determined that the products of this transformation include a cyclic urea, a ring‐opened formamide and a bis‐carbene copper(I) complex. These results illustrate the potential of NHCs to functionalize a much broader class of metals, including those prone to oxidation, greatly facilitating the preparation of NHC‐based films on metals other than gold.
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