Probing Solvent-Ligand Interactions in Colloidal Nanocrystals by the NMR Line Broadening

Although solvent-ligand interactions play a major role in nanocrystal synthesis, dispersion formulation, and assembly, there is currently no direct method to study this. Here we examine the broadening of H-1 NMR resonances associated with bound ligands and turn this poorly understood descriptor into a tool to assess solvent-ligand interactions. We show that the line broadening has both a homogeneous and a heterogeneous component. The former is nanocrystal-size dependent, and the latter results from solvent-ligand interactions. Our model is supported by experimental and theoretical evidence that correlates broad NMR lines with poor ligand solvation. This correlation is found across a wide range of solvents, extending from water to hexane, for both hydrophobic and hydrophilic ligand types, and for a multitude of oxide, sulfide, and selenide nanocrystals. Our findings thus put forward NMR line-shape analysis as an indispensable tool to form, investigate, and manipulate nanocolloids.