Spectroscopic Determination of Site-Selective Ligand Binding on Single Anisotropic Nanocrystals

Organic surface ligands are integral components of nanocrystals and nanoparticles that have a strong influence on their physicochemical properties, their interaction with the environment, and their ability to self-assemble and order into higher-order structures. These hybrid nanomaterials are tunable with applications in catalysis, directed self-assembly, next-generation optoelectronics, and chemical and quantum sensing. Critically, future advances depend on our ability to rationally engineer their surface chemistry. However, fundamental knowledge of ligand-nanoparticle behavior is limited by uncertainty in where and how these ligands bind to surfaces. For nanoparticles, in particular, few characterization techniques offer both the high spatial resolution and the precise chemical mapping needed to identify specific ligand binding sites. In this study, we utilized synchrotron infrared nanospectroscopy (SINS), atomic force microscopy (AFM), and scanning tunneling microscopy (STM) together with first-principles computer simulations to validate the site-selective adsorption of organic ligands on a shaped nanocrystal surface. Specifically, we demonstrate that the sterically encumbered isocyanide ligands (CNAr^{Mes2}) preferentially bind to the high curvature features of Ag nanocubes (NCs), where low-coordinate Ag atoms are present. In contrast, isocyanide ligands that do not exhibit these steric properties show no surface selectivity. SINS serves as an effective tool to validate these surface binding interactions at the near-single molecule level. These results indicate that steric effects can be successfully harnessed to design bespoke organic ligands for fine-tuning nanocrystal surface chemistry and the properties of the nanocrystal ligand shell.