title: Multinuclear solid-state NMR spectroscopy of doped lanthanum fluoride nanoparticles.
abstract: Multinuclear solid-state NMR spectroscopy and powder X-ray diffraction (XRD) experiments are applied to comprehensively characterize a series of pure and lanthanide-doped LaF3 nanoparticles (NPs) that are capped with di-n-octadectyldithiophosphate ligands (Ln3+ = diamagnetic Y3+ and Sc3+ and paramagnetic Yb3+ ions), as well as correlated bulk microcrystalline materials (LaF3, YF3, and ScF3). Solid-state 139La and 19F NMR spectroscopy of bulk LaF3 and the LaF3 NPs reveal that the inorganic core of the NP retains the LaF3 structure at the molecular level; however, inhomogeneous broadening of the NMR powder patterns arises from distributions of 139La and 19F NMR interactions, confirming a gradual change in the La and F site environments from the NP core to the surface. 139La and 19F NMR experiments also indicate that low levels (5 and 10 mol %) of Ln3+ doping do not significantly change the LaF3 structure in the NP core. Similar doping levels of paramagnetic Yb3+ ions severely broaden 19F resonances, but only marginally effect 139La powder patterns, suggesting that the dopant ions are uniformly distributed throughout the NP core and occupy vacant La sites. Measurements of 139La T1 and T2 relaxation constants are seen to vary between the bulk material and NPs and between samples with diamagnetic and paramagnetic dopants. 45Sc NMR experiments confirm that the dopants are integrated into the La sites of the LaF3 core. Solid-state 1H and 31P magic-angle spinning (MAS) NMR spectra aid in probing the nature of the capping ligands and their interactions at the NP surface. 31P cross-polarization (CP)/MAS NMR experiments identify not only the dithiophosphate head groups but also thiophosphate and phosphate species which may form during NP synthesis. Finally, 19F-31P CP/MAS and 1H MAS experiments confirm that ligands are coordinated to the NP surface.
authors: Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario, Canada N9B 3P4.
authors: Andy Y H
authors: AY
authors: Lo
authors: Vasanthakumaran
authors: V
authors: Sudarsan
authors: Sri
authors: S
authors: Sivakumar
authors: Frank
authors: F
authors: van Veggel
authors: Robert W
authors: RW
authors: Schurko
mesh_terms: D002412:Cations / Q000737:chemistry; D005459:Fluorides / Q000737:chemistry*; D007811:Lanthanum / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D053758:Nanoparticles / Q000737:chemistry*; D014961:X-Ray Diffraction; D015019:Yttrium / Q000737:chemistry
chemical_list: D002412:Cations; D008024:Ligands; C083668:lanthanum trifluoride; D015019:Yttrium; D007811:Lanthanum; D005459:Fluorides