67Zn NMR investigation of zinc halides

Bastow, Timothy J.

doi:10.1016/j.cplett.2003.09.065

Cited by 14 publications

(8 citation statements)

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“…Table summarizes all 67 Zn SSNMR data that have been reported to date. These data include NMR studies on metallic zinc, − numerous simple inorganic compounds, − 19 small organozinc complexes, ,− and five zinc-containing macromolecules. ,− The data in Table have been classified according to the zinc coordination geometry in each system. Aside from zinc metal, which has a hexagonal close-packed structure, all other zinc atoms are found in sites of tetrahedral or octahedral coordination, with the former being more abundant.…”

Section: Introductionmentioning

confidence: 99%

High-Field Solid-State ⁶⁷Zn NMR Spectroscopy of Several Zinc−Amino Acid Complexes

Mroué

Power

2009

J. Phys. Chem. A

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We report the results of our solid-state (67)Zn NMR study of the various zinc sites in four zinc-amino acid coordination complexes: bis(glycinato)zinc(II) monohydrate; bis(l-alaninato)zinc(II); bis(l-histidinato)zinc(II) dihydrate; and sodium bis(l-cysteinato)zincate(II) hexahydrate; as well as a related complex, bis(imidazole)zinc(II) chloride. We demonstrate the advantages of using high (21.1 T) applied magnetic fields for detecting (67)Zn directly at ambient temperatures using the quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) pulse sequence. The stepped-frequency technique was employed in cases where the central-transition (CT) (67)Zn NMR spectra were too broad to be uniformly excited. The parameters of the anisotropic zinc tensors were extracted by iterative simulations of the experimental spectra. In all cases, the quadrupolar interaction is found to dominate the central-transition (67)Zn NMR spectra; no convincing effects from chemical shift anisotropy (CSA) on the NMR spectra of the five complexes could be reliably detected at this field strength. Analyses of the experimental NMR spectra reveal that the (67)Zn quadrupolar coupling constants (C(Q)) range from 7.05 to 26.4 MHz, the isotropic chemical shifts (delta(iso)) range from 140 to 265 ppm, and the quadrupolar asymmetry parameters (eta(Q)) range from 0.20 to 0.95. The first report of the NMR spectral features of pentacoordinated zinc sites is included for two complexes. Quantum chemical calculations of the electric field gradient (EFG) and magnetic shielding tensors reproduced the experimental results to a reasonable extent. Moreover, the computationally determined orientations of both tensors permit correlations between NMR tensor properties and zinc local environments to be understood.

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Section: Introductionmentioning

confidence: 99%

High-Field Solid-State ⁶⁷Zn NMR Spectroscopy of Several Zinc−Amino Acid Complexes

Mroué

Power

2009

J. Phys. Chem. A

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“…are able to provide quadrupolar parameters from structural data with good accuracy. The WIEN2k code was proven to be very efficient and reliable. − A key step in the success of these calculations is the optimization of the structures: the atomic positions of the atoms are adjusted, keeping the cell parameters unchanged, until the forces acting on the atoms are minimized. This optimization step is especially important for compounds whose structures were determined from powder diffraction data. − Finally, by a comparison of experimental and calculated data, a bijective attribution of the NMR resonance lines to the crystallographic sites can be achieved.…”

Section: Introductionmentioning

confidence: 99%

Multinuclear High-Resolution NMR Study of Compounds from the Ternary System NaF−CaF₂−AlF₃: from Determination to Modeling of NMR Parameters

et al. 2006

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27Al and 23Na NMR satellite transition spectroscopy and 3Q magic-angle-spinning spectra are recorded for three compounds from the ternary NaF-CaF2-AlF3 system. The quadrupolar frequency nuQ, asymmetry parameter etaQ, and isotropic chemical shift deltaiso are extracted from the spectrum reconstructions for five aluminum and four sodium sites. The quadrupolar parameters are calculated using the LAPW-based ab initio code WIEN2k. It is necessary to perform a structure optimization of all compounds to ensure a fine agreement between experimental and calculated parameters. By a comparison of experimental and calculated values, an attribution of all of the 27Al and 23Na NMR lines to the crystallographic sites is achieved. High-speed 19F NMR MAS spectra are recorded and reconstructed for the same compounds, leading to the determination of 18 isotropic chemical shifts. The superposition model developed by Bureau et al. is used, allowing a bijective assignment of the 19F NMR lines to the crystallographic sites.

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“…Solid-state 77 Se NMR has previously been used to characterize surface and local structures of chalcogenides [14], including nanoparticles [15,16]. By comparison, there have been far fewer studies of inorganic materials using solid-state 67 Zn NMR [14,17,18], due in part to the low gyromagnetic ratio, low natural abundance, and the quadrupolar character of 67 Zn, which result in low signal sensitivity and poor spectral resolution, which are both significantly improved at very high magnetic fields.…”

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Atomic Positional Versus Electronic Order in Semiconducting ZnSe Nanoparticles

et al. 2009

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Size-controlled ZnSe nanoparticles with high extents of atomic positional order are shown to exhibit large size-dependent variations in their local electronic environments. Solid-state ;{77}Se and ;{67}Zn NMR spectra reveal increasingly broad distributions of ;{77}Se and ;{67}Zn environments with decreasing nanoparticle sizes, in contrast with high degrees of atomic positional order established by transmission electron microscopy and x-ray diffraction. First-principles calculations of NMR parameters distinguish between atomic positional and electronic disorder that propagate from the nanoparticle surfaces and yield insights on the order and disorder present.

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67Zn NMR investigation of zinc halides

Cited by 14 publications

References 13 publications

High-Field Solid-State ⁶⁷Zn NMR Spectroscopy of Several Zinc−Amino Acid Complexes

High-Field Solid-State ⁶⁷Zn NMR Spectroscopy of Several Zinc−Amino Acid Complexes

Multinuclear High-Resolution NMR Study of Compounds from the Ternary System NaF−CaF₂−AlF₃: from Determination to Modeling of NMR Parameters

Atomic Positional Versus Electronic Order in Semiconducting ZnSe Nanoparticles

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67Zn NMR investigation of zinc halides

Cited by 14 publications

References 13 publications

High-Field Solid-State 67Zn NMR Spectroscopy of Several Zinc−Amino Acid Complexes

High-Field Solid-State 67Zn NMR Spectroscopy of Several Zinc−Amino Acid Complexes

Multinuclear High-Resolution NMR Study of Compounds from the Ternary System NaF−CaF2−AlF3: from Determination to Modeling of NMR Parameters

Atomic Positional Versus Electronic Order in Semiconducting ZnSe Nanoparticles

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High-Field Solid-State ⁶⁷Zn NMR Spectroscopy of Several Zinc−Amino Acid Complexes

High-Field Solid-State ⁶⁷Zn NMR Spectroscopy of Several Zinc−Amino Acid Complexes

Multinuclear High-Resolution NMR Study of Compounds from the Ternary System NaF−CaF₂−AlF₃: from Determination to Modeling of NMR Parameters