NMR Characterization of Nanoscale Surface Patterning in Mixed Ligand Nanoparticles.

Spontaneous phase separation in binary mixed ligand shells is a proposed strategy to create patchy nanoparticles. The surface anisotropy, providing directionality along with interfacial properties emerging from both ligands, is highly desirable for targeted drug delivery, catalysis, and other applications. However, characterization of phase separation on the nanoscale remains quite challenging. Here we have adapted solid-state 1H spin diffusion NMR experiments designed to detect and quantify spatial heterogeneity in polymeric materials to nanoparticles (NPs) functionalized with mixed short ligands. Janus NPs and physical mixtures of homoligand 3.5 nm diameter ZrO2 NPs, with aromatic (phenylphosphonic acid, PPA) and aliphatic (oleic acid, OA) ligands, were used to calibrate the 1H spin diffusion experiments. The Janus NPs, prepared by a facile wax/water Pickering emulsion method, and mixed ligand NPs, produced by ligand exchange, both with 1:1 PPA:OA ligand compositions, display strikingly different solvent and particle-particle interactions. 1H spin diffusion NMR experiments are most consistent with a lamellar surface pattern for the mixed ligand ZrO2 NPs. Solid-state 1H spin diffusion NMR is shown to be a valuable additional characterization tool for mixed ligand NPs, as it not only detects the presence of nanoscale phase separation but also allows measurement of the domain sizes and geometries of the surface phase separation.

Effect of the π-bridge on the light absorption and emission in push-pull coumarins and on their supramolecular organization.

A family of eight π-extended push-pull coumarins with cross-conjugated (amide) and directly conjugated (p-phenylene, alkyne, alkene) bridges were synthesized through a convergent strategy. Using an experimentally calibrated computational protocol, their UV-Visible light absorption and emission spectra in solution were investigated. Remarkably, amide-, alkyne- and alkene-bridges undergo comparable vertical excitations. The different nature of these bridges manifests during excited-state relaxation and fluorescence. We predict that these molecules can serve as building blocks for p-type semiconductors with low reorganization energies, below 0.2 eV. Since solid-state self-assembly is crucial for this application, we examined the effect of the π-bridge over the supramolecular organization in this family of compounds to determine if stacking prevails in these π-extended coumarin derivatives. Amide and alkyne spacers allow coplanar conformations which crystallize readily; p-phenylene hinders planarity yet allows facile crystallization; alkene-bridged molecules eluded all crystallization attempts. All the crystals obtained feature dense face-to-face π-stacking with 3.5-3.7 Å interlayer distances, expected to facilitate charge transfer processes in the solid state.