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

摘要

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 (Cu 6 (SC 7 H 4 NO) 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 H 2 O 2 .