Single Crystal Sub‐Nanometer Sized Cu₆(SR)₆ Clusters: Structure, Photophysical Properties, and Electrochemical Sensing

Abstract

Organic ligand‐protected metal nanoclusters have attracted extensively attention owing to their atomically precise composition, determined atom‐packing structure and the fascinating properties and promising applications. To date, most research has been focused on thiol‐stabilized gold and silver nanoclusters and their single crystal structures. Here the single crystal copper nanocluster species (Cu6(SC7H4NO)6) determined by X‐ray crystallography and mass spectrometry is presented. The hexanuclear copper core is a distorted octahedron surrounded by six mercaptobenzoxazole ligands as protecting units through a simple bridging bonding motif. Density functional theory (DFT) calculations provide insight into the electronic structure and show the cluster can be viewed as an open‐shell nanocluster. The UV–vis spectra are analyzed using time‐dependent DFT and illustrates high‐intensity transitions involving primarily ligand states. Furthermore, the as‐synthesized copper clusters can serve as promising nonenzymatic sensing materials for high sensitive and selective detection of H2O2.

Multinuclear Cu(I) Clusters Featuring a New Triply Bridging Coordination Mode of Phosphaamidinate Ligands

“…24 The cluster type F consists of two 6-coordinate Cu(II) trimer units bridged by two nitrate ions, 25 while G possesses a coplanar assembly of 5-coordinate Cu(II) atoms. 26 Octahedral or distorted octahedral assemblies are common for hexanuclear Cu(I) clusters as evidenced by clusters H , 27 I , 28 and J . 29 In contrast, the arrangement of Cu(I) atoms in 3 defines an antiprism rather than an octahedron.…”

Nitrogen-Rich Polyacrylonitrile-Based Graphitic Carbons for Hydrogen Peroxide Sensing

“…Among these, electrochemical detection, in general, has the reputation of having high sensitivity, selectivity, and affordability. However, early experiments of H 2 O 2 sensing used noble metals, such as platinum and gold as catalytic surface for attaining high sensitivity, making the electrochemical detection of H 2 O 2 an expensive option [ 8 , 9 , 10 ]. This has eventually led to the use of various carbon allotropes, such as pure graphene, carbon nanotubes, and graphite for this purpose, which not only circumvents the use of expensive noble metals but also allows for a non-enzymatic method of sensing [ 11 , 12 , 13 , 14 , 15 ].…”

Copper nanoclusters: designed synthesis, structural diversity, and multiplatform applications

“…Within this category, Wei Chen and co-workers in 2016 reported the synthesis and the structure of a small Cu6(SR)6 cluster protected with 2-mercaptobenzoxazole ligand from the reduction of a reaction mixture with sodium borohydride (Scheme 3a). 151 The Cu6 core has an octahedral geometry and is protected by six SR-units through a bridging bonding motif (Fig. 11 A).…”