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

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journal contribution
posted on 03.08.2018 by Jonathan De Roo, Nuri Yazdani, Emile Drijvers, Alessandro Lauria, Jorick Maes, Jonathan S. Owen, Isabel Van Driessche, Markus Niederberger, Vanessa Wood, Jose C. Martins, Ivan Infante, Zeger Hens
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 1H 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.