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Blind spheres of paramagnetic dopants in solid state NMR

(2019) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 21(19). p.10185-10194
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Abstract
Solid-state NMR on paramagnetically doped crystal structures gives information about the spatial distribution of dopants in the host. Paramagnetic dopants may render NMR active nuclei virtually invisible by relaxation, paramagnetic broadening or shielding. In this contribution blind sphere radii r(0) have been reported, which could be extracted through fitting the NMR signal visibility function f (x) = exp(-ar(0)(3)x) to experimental data obtained on several model compound series: La(1-x)Ln(x)PO(4) (Ln = Nd, Sm, Gd, Dy, Ho, Er, Tm, Yb), Sr1-xEuxGa2S4 and (Zn1-xMnx)(3)(PO4)(2)center dot 4H(2)O. Radii were extracted for H-1, P-31 and Ga-71, and dopants like Nd3+, Gd3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+ and Mn2+. The observed radii determined differed in all cases and covered a range from 5.5 to 13.5 angstrom. While these radii were obtained from the amount of invisible NMR signal, we also show how to link the visibility function to lineshape parameters. We show under which conditions empirical correlations of linewidth and doping concentration can be used to extract blind sphere radii from second moment or linewidth parameter data. From the second moment analysis of La1-xSmxPO4 P-31 MAS NMR spectra for example, a blind sphere size of Sm3+ can be determined, even though the visibility function remains close to 100% over the entire doping range. Dependence of the blind sphere radius r(0) on the NMR isotope and on the paramagnetic dopant could be suggested and verified: for different nuclei, r(0) shows a 3 root gamma-dependence, gamma being the gyromagnetic ratio. The blind sphere radii r(0) for different paramagnetic dopants in a lanthanide series could be predicted from the pseudo-contact term.
Keywords
MAGNETIC-RESONANCE SHIFTS, SPIN-LATTICE-RELAXATION, LOCAL ENVIRONMENTS, MAS NMR, BATTERY CATHODES, RED PHOSPHOR, O-17 NMR, LUMINESCENCE, SPECTROSCOPY, DYNAMICS

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Citation

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MLA
Li, Wenyu, et al. “Blind Spheres of Paramagnetic Dopants in Solid State NMR.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS, vol. 21, no. 19, 2019, pp. 10185–94.
APA
Li, W., Zhang, Q., Joos, J., Smet, P., & Schmedt auf der Günne, J. (2019). Blind spheres of paramagnetic dopants in solid state NMR. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 21(19), 10185–10194.
Chicago author-date
Li, Wenyu, Qianyun Zhang, Jonas Joos, Philippe Smet, and Jörn Schmedt auf der Günne. 2019. “Blind Spheres of Paramagnetic Dopants in Solid State NMR.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 21 (19): 10185–94.
Chicago author-date (all authors)
Li, Wenyu, Qianyun Zhang, Jonas Joos, Philippe Smet, and Jörn Schmedt auf der Günne. 2019. “Blind Spheres of Paramagnetic Dopants in Solid State NMR.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 21 (19): 10185–10194.
Vancouver
1.
Li W, Zhang Q, Joos J, Smet P, Schmedt auf der Günne J. Blind spheres of paramagnetic dopants in solid state NMR. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2019;21(19):10185–94.
IEEE
[1]
W. Li, Q. Zhang, J. Joos, P. Smet, and J. Schmedt auf der Günne, “Blind spheres of paramagnetic dopants in solid state NMR,” PHYSICAL CHEMISTRY CHEMICAL PHYSICS, vol. 21, no. 19, pp. 10185–10194, 2019.
@article{8629774,
  abstract     = {Solid-state NMR on paramagnetically doped crystal structures gives information about the spatial distribution of dopants in the host. Paramagnetic dopants may render NMR active nuclei virtually invisible by relaxation, paramagnetic broadening or shielding. In this contribution blind sphere radii r(0) have been reported, which could be extracted through fitting the NMR signal visibility function f (x) = exp(-ar(0)(3)x) to experimental data obtained on several model compound series: La(1-x)Ln(x)PO(4) (Ln = Nd, Sm, Gd, Dy, Ho, Er, Tm, Yb), Sr1-xEuxGa2S4 and (Zn1-xMnx)(3)(PO4)(2)center dot 4H(2)O. Radii were extracted for H-1, P-31 and Ga-71, and dopants like Nd3+, Gd3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+ and Mn2+. The observed radii determined differed in all cases and covered a range from 5.5 to 13.5 angstrom. While these radii were obtained from the amount of invisible NMR signal, we also show how to link the visibility function to lineshape parameters. We show under which conditions empirical correlations of linewidth and doping concentration can be used to extract blind sphere radii from second moment or linewidth parameter data. From the second moment analysis of La1-xSmxPO4 P-31 MAS NMR spectra for example, a blind sphere size of Sm3+ can be determined, even though the visibility function remains close to 100% over the entire doping range. Dependence of the blind sphere radius r(0) on the NMR isotope and on the paramagnetic dopant could be suggested and verified: for different nuclei, r(0) shows a 3 root gamma-dependence, gamma being the gyromagnetic ratio. The blind sphere radii r(0) for different paramagnetic dopants in a lanthanide series could be predicted from the pseudo-contact term.},
  author       = {Li, Wenyu and Zhang, Qianyun and Joos, Jonas and Smet, Philippe and Schmedt auf der Günne, Jörn},
  issn         = {1463-9076},
  journal      = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS},
  keywords     = {MAGNETIC-RESONANCE SHIFTS,SPIN-LATTICE-RELAXATION,LOCAL ENVIRONMENTS,MAS NMR,BATTERY CATHODES,RED PHOSPHOR,O-17 NMR,LUMINESCENCE,SPECTROSCOPY,DYNAMICS},
  language     = {eng},
  number       = {19},
  pages        = {10185--10194},
  title        = {Blind spheres of paramagnetic dopants in solid state NMR},
  url          = {http://dx.doi.org/10.1039/c9cp00953a},
  volume       = {21},
  year         = {2019},
}

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