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

摘要

Organic ligand-protected metal nanoclusters have attracted extensivelyattention owing to their atomically precise composition, determinedatom-packing structure and the fascinating properties and promisingapplications. To date, most research has been focused on thiol-stabilizedgold and silver nanoclusters and their single crystal structures. Here thesingle crystal copper nanocluster species (Cu6(SC7H4NO)6) determined byX-ray crystallography and mass spectrometry is presented. The hexanuclearcopper core is a distorted octahedron surrounded by six mercaptobenzoxazoleligands as protecting units through a simple bridging bondingmotif. Density functional theory (DFT) calculations provide insight into theelectronic structure and show the cluster can be viewed as an open-shellnanocluster. The UV–vis spectra are analyzed using time-dependent DFTand illustrates high-intensity transitions involving primarily ligand states.Furthermore, the as-synthesized copper clusters can serve as promisingnonenzymatic sensing materials for high sensitive and selective detectionof H2O2.