Hexanethiolate Monolayer Protected 38 Gold Atom Cluster

Abstract

The nucleation−growth−passivation Brust reaction has been modified so as to enrich the product in useful quantities of a 38-atom gold nanoparticle coated with a hexanethiolate monolayer. Two modifications are described, using −78 °C reduction temperature and a hyperexcess of thiol. Compositional evidence is presented that establishes the product as a Au₃₈(C6)₂₄ hexanethiolate monolayer protected cluster (MPC), based on transmission electron microscopy, laser ionization−desorption mass spectrometry, thermogravimetric analysis, and elemental analysis. Reverse phase HPLC confirms the relatively good monodispersity of the MPC products, but high-resolution double-column HPLC reveals that the MPCs are a mixture of closely related but chromatographically distinct products. Voltammetry, low energy spectrophotometry, and spectroelectrochemistry reveal, respectively, a 1.6 eV electrochemical energy gap between the first oxidation and the first reduction, an optical HOMO−LUMO energy absorbance edge at 1.3 eV, and a bleaching of optical absorbance near the 1.3 eV band edge that accompanies electrochemical oxidation of the nanoparticle.