Preparation, Characterization, and Chemical Stability of Gold Nanoparticles Coated with Mono-, Bis-, and Tris-Chelating Alkanethiols

A systematically varying series of monolayer-protected clusters (MPCs) was prepared by exposing small gold nanoparticles (∼2 nm in diameter) to the following four adsorbates: n-octadecanethiol ( n -C18), 2-hexadecylpropane-1,3-dithiol (C18C2), 2-hexadecyl-2-methylpropane-1,3-dithiol (C18C3), and 1,1,1-tris(mercaptomethyl)heptadecane ( t -C18). The resultant MPCs were characterized by solubility studies, UV-vis spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FT-IR). All of the MPCs were soluble in common organic solvents; moreover, analysis by TEM showed that the core dimensions were unaffected by exposure to any of the adsorbates. Separate studies by XPS revealed that the sulfur atoms in all MPCs were predominantly bound to the surface of gold (i.e., ∼85% or better). Analysis by FT-IR showed that MPCs functionalized with n -C18 possessed alkyl chains having the greatest conformational order in both the solid-state and dispersed in solution; in contrast, those generated from the other three adsorbates were more liquid-like with reduced conformational order (or crystallinity). The rate of nanoparticle decomposition induced by cyanide ions was monitored by UV−vis spectroscopy. While MPCs functionalized with n -C18 showed the fastest rate of decomposition, those functionalized with C18C3 were the most resistant to decomposition. Overall, the following trend in chemical stability was observed, C18C3 ≫ C18C2 > t -C18 ≫ n -C18.