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Surface functionalization of nanoparticles (NPs) plays a crucial role in particle solubility and reactivity. It is vital for particle nucleation and growth as well as for catalysis. This raises the quest for functionalization efficiency and new approaches to probe the degree of surface coverage. We present an (in situ) proton nuclear magnetic resonance (1H NMR) study on the ligand exchange of oleylamine by 1-octadecanethiol as a function of the particle size and repeated functionalization on Au NPs. Ligand exchange is an equilibrium reaction associated with Nernst distribution, which often leads to incomplete surface functionalization following “standard” literature protocols. Here, we show that the surface coverage with the ligand depends on the (i) repeated exchange reactions with large ligand excess, (ii) size of NPs, that is, the surface curvature and reactivity, and (iii) molecular size of the ligand. As resonance shifts and extensive line broadening during and after the ligand exchange impede the evaluation of 1H NMR spectra, one- and two-dimensional 19F NMR techniques (correlation spectroscopy and diffusion ordered spectroscopy) with 1H,1H,2H,2H-perfluorodecanthiol as the fluorinated thiol ligand were employed to study the reactions. The enhanced resolution associated with the spectral range of the 19F nucleus allowed carrying out a site-specific study of thiol chemisorption. The widths and shifts of the resonance signals of the different fluorinated carbon moieties were correlated with the distance to the thiol anchor group. In addition, the diffusion analysis revealed that moieties closer to the NP surface are characterized by a broader diffusion coefficient distribution as well as slower diffusion. [ABSTRACT FROM AUTHOR]

The self-assembly, the molecular dynamics, and the kinetics of structure formation are studied in dipole-functionalized hexabenzocoronene (HBC) derivatives. Dipole substitution destabilizes the columnar crystalline phase except for the dimethoxy- and monoethynyl-substituted HBCs that undergo a reversible transformation to the crystalline phase. The disk dynamics are studied by dielectric spectroscopy and site- specific NMR techniques that provide both the time-scale and geometry of motion. Application of pressure results in the thermodynamic phase diagram that shows increasing stability of the crystalline phase at elevated pressures. Long-lived metastability was found during the transformation between the two phases. These results suggest new thermodynamic and kinetic pathways that favor the phase with the highest charge carrier mobility. [ABSTRACT FROM AUTHOR]

Modifying the surfaces of metal oxide nanoparticles (NPs) with monolayers of ligands provides a simple and direct method to generate multifunctional coatings by altering their surface properties. This works best if the composition of the monolayers can be controlled. Mussel-inspired, noninnocent catecholates stand out from other ligands like carboxylates and amines because they are redox-active and allow for highly efficient surface binding and enhanced electron transfer to the surface. However, a comprehensive understanding of their surface chemistry, including surface coverage and displacement of the native ligand, is still lacking. Here, we unravel the displacement of oleate (OA) ligands on hydrophobic, OA-stabilized TiO 2 NPs by catecholate ligands using a combination of one- and two-dimensional nuclear magnetic resonance (NMR) spectroscopy techniques. Conclusive pictures of the ligand shells before and after surface modification with catecholate were obtained by 1 H and 13 C NMR spectroscopy (the 13 C chemical shift being more sensitive and with a broader range). The data could be explained using a Langmuir-type approach. Gradual formation of a mixed ligand shell was observed, and the surface processes of catecholate adsorption and OA desorption were quantified. Contrary to the prevailing view, catecholate displaces only a minor fraction (∼20%) of the native OA ligand shell. At the same time, the total ligand density more than doubled from 2.3 nm -2 at native oleate coverage to 4.8 nm -2 at maximum catecholate loading. We conclude that the catecholate ligand adsorbs preferably to unoccupied Ti surface sites rather than replacing native OA ligands. This unexpected behavior, reminiscent of the Vroman effect for protein corona formation, appears to be a fundamental feature in the widely used surface modification of hydrophobic metal oxide NPs with catecholate ligands. Moreover, our findings show that ligand displacement on OA-capped TiO 2 NPs is not suited for a full ligand shell refunctionalization because it produces only mixed ligand shells. Therefore, our results contribute to a better understanding and performance of photocatalytic applications based on catecholate ligand-sensitized TiO 2 NPs.