Here we synthesize 2-ethylhexyl, 2-hexyldecyl, 2-[2-(2-methoxyethoxy)ethoxy]ethyl, oleyl and n-octadecyl phosphonic acid and use them to functionalize CdSe and HfO2 nanocrystals. In contrast to branched carboxylic acids, post-synthetic surface functionalization of CdSe and HfO2 nanocrystals is readily achieved with branched phosphonic acids. Phosphonic acid capped HfO2 nanocrystals are subsequently evaluated as memristor using conductive atomic force microscopy (c-AFM). We find that 2-ethylhexyl phosphonic acid is a superior ligand, combining a high colloidal stability with a compact ligand shell that results in a record-low operating voltage that is promising for application in flexible electronics.

Iron oxide and hafnium oxide nanocrystals are two of the few successful examples of inorganic nanocrystals used in a clinical setting. Although crucial to their application, their aqueous surface chemistry is not fully understood. The literature contains conflicting reports regarding the optimum binding group. To alleviate these inconsistencies, we set out to systematically investigate the interaction of carboxylic acids, phosphonic acids, and catechols to metal oxide nanocrystals in polar media. Using nuclear magnetic resonance spectroscopy and dynamic light scattering, we map out the pHdependent binding affinity of the ligands toward hafnium oxide nanocrystals (an NMR-compatible model system). Carboxylic acids easily desorb in water from the surface and only provide limited colloidal stability from pH 2 to pH 6. Phosphonic acids, on the other hand, provide colloidal stability over a broader pH range but also feature a pH-dependent desorption from the surface. They are most suited for acidic to neutral environments (pH <8). Finally, nitrocatechol derivatives provide a tightly bound ligand shell and colloidal stability at physiological and basic pH (6−10). Whereas dynamically bound ligands (carboxylates and phosphonates) do not provide colloidal stability in phosphate-buffered saline, the tightly bound nitrocatechols provide long-term stability. We thus shed light on the complex ligand binding dynamics on metal oxide nanocrystals in aqueous environments. Finally, we provide a practical colloidal stability map, guiding researchers to rationally design ligands for their desired application.

<p>Here we synthesize 2-ethylhexyl, 2-hexyldecyl, 2-[2-(2-methoxyethoxy)ethoxy]ethyl, oleyl and <i>n</i>-octadecyl phosphonic acid and use them to functionalize CdSe and HfO₂ nanocrystals. In contrast to branched carboxylic acids, post-synthetic surface functionalization of CdSe and HfO₂ nanocrystals is readily achieved with branched phosphonic acids. A simple flow coating process is used to deposit ribbons of individual phosphonic acid capped HfO₂ nanocrystals, which are subsequently evaluated as a memristor using conductive atomic force microscopy (c-AFM). We find that 2-ethylhexyl phosphonic acid is a superior ligand, combining a high colloidal stability with a compact ligand shell that results in a record-low operating voltage that is promising for application in flexible electronics. </p>

We recently introduced monoalkyl phosphinic acids as a ligand class for nanocrystal (NC) synthesis. Their metal salts have interesting reactivity differences compared to metal carboxylates and phosphonates and provide a cleaner work-up compared to phosphonates. However, little is known about the surface chemistry of NCs with monoalkyl phosphinate ligands. Here, we probe the relative binding affinity of monoalkyl phosphinate ligands with respect to other X-type ligands. We perform competitive ligand exchange reactions with carboxylate and phosphonate ligands at the surface of hafnia, cadmium selenide, and zinc sulfide NCs. We monitor the ligand shell composition by solution 1 H and 31 P NMR spectroscopy. Using a monoalkyl phosphinic acid with an ether functionality, we gain an additional NMR signature, apart from the typical alkene resonance in oleic acid and oleylphosphonic acid. We find that carboxylate ligands are easily exchanged upon exposure to monoalkyl phosphinic acids, whereas an equilibrium is reached between monoalkyl phosphinates and phosphonates, slightly in the favor of phosphonate (K = 2). Phosphinic acids have thus an intermediate binding affinity between carboxylic acids and phosphonic acids for all the NCs studied. These results enable the sophisticated use of monoalkyl phosphinic acids for NC synthesis and for post-synthetic surface engineering.