Ligand Control over the Electronic Properties within the Metallic Core of Gold Nanoparticles

The behavior of electrons within the metallic core of gold nanoparticles (AuNPs) can be controlled by the nature of the surface chemistry of the AuNPs. Specifically, the conduction electron spin resonance (CESR) spectra of AuNPs of diameter 1.8–1.9 nm are sensitive to ligand exchange of hexanethiol for 4‐bromothiophenol on the surface of the nanoparticle. Chemisorption of the aromatic ligand leads to a shift in the metallic electron’s g‐factor toward the value expected for pure gold systems, suggesting an increase in metallic character for the electrons within the gold core. Analysis by UV/Vis absorption spectroscopy reveals a concomitant bathochromic shift of the surface plasmon resonance band of the AuNP, indicating that other electronic properties of AuNPs are also affected by the ligand exchange. In total, our results demonstrate that the chemical nature of the ligand controls the valence band structure of AuNPs.