23Na NMR Spectroscopy of Solids: Interpretation of Quadrupole Interaction Parameters and Chemical Shifts

Koller, Hubert; Engelhardt, G.; Kentgens, A.P.M.; Sauer, Joachim

doi:10.1021/j100057a004

Cited by 285 publications

(328 citation statements)

References 7 publications

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“…Koller et al calculated the C Q values by using point charge model for coordination structure of Na and oxygen, and concluded that the C Q value, which is zero for regular tetrahedral or octahedral coordinations, has moderate values for trigonal bipyramidal or quadratic pyramidal structure, and show much larger value for planner structures with four or six oxygens around Na [6]. Hence, it is considered that the Na C ions are located in the hexagonal cavities in the dry sample, and with increasing water content the Na C ions are hydrated and their hydration structures are changed from planner to octahedral.…”

Section: Resultsmentioning

confidence: 99%

A study on hydration behaviors of interlayer cations in montmorillonite by solid state NMR

Ohkubo

Saito

Kanehashi

et al. 2004

Science and Technology of Advanced Materials

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Solid state 23 Na NMR spectra of Na-montmorillonite under dry and hydrated conditions have been measured to study hydration structure of Na C in interlayer spaces. The 23 Na triple quantum (3Q) MAS NMR experiments have been performed to determine the quadrupole coupling constants (C Q ) and the isotropic chemical shifts (d iso ). The C Q values were found to remarkably depend on water content, i.e. the C Q values increase with changing from dry condition to hydrated one (at around 12.5 wt% water content) and gradually decrease with an increase in the water content. Since the C Q value is a sensitive parameter to the local structure of the nucleus measured, the changes in C Q values with water content should correspond to those in the hydration structure of Na C in the interlayer spaces. Thus, it is considered that the increment of the C Q value in the water content of 12.5 wt% is due to the formation of hydrated Na C with planner structure, and that the decrease in C Q values with the water content is attributed to the formation of hydrated Na C with spherical symmetric structure. q

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Section: Resultsmentioning

confidence: 99%

A study on hydration behaviors of interlayer cations in montmorillonite by solid state NMR

Ohkubo

Saito

Kanehashi

et al. 2004

Science and Technology of Advanced Materials

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“…1,13,14 Studies of systematic series of ternary vanadium complexes that are known to contain two different coordinating ligand systems can assist in gauging the effect of ligand substitution on the chemistry at the vanadium center. Solid-state 51 V NMR has the potential to yield a threedimensional description of the local vanadium environment and of the possible changes that take place in the molecular orbitals and electrostatic structure at the vanadium when the coordinating ligands are changed. 3, 15, 16, 17, 18, 19 , 20 , Many inorganic vanadium-containing coordination complexes have been studied using 51 V SSNMR.…”

Section: Introductionmentioning

confidence: 99%

“…Solid-state 51 V NMR has the potential to yield a threedimensional description of the local vanadium environment and of the possible changes that take place in the molecular orbitals and electrostatic structure at the vanadium when the coordinating ligands are changed. 3, 15, 16, 17, 18, 19 , 20 , Many inorganic vanadium-containing coordination complexes have been studied using 51 V SSNMR. 21,22,23 The investigations of vanadium organometallic and coordination compounds have illustrated that valuable information about the molecular and electronic structure can be obtained by measuring the anisotropy of the 51 V chemical shift tensor and the electric field gradient (EFG) tensor; 51 V is a spin I = 7/2 quadrupolar nucleus.…”

Section: Introductionmentioning

confidence: 99%

Investigating the Vanadium Environments in Hydroxylamido V(V) Dipicolinate Complexes Using ⁵¹V NMR Spectroscopy and Density Functional Theory

et al. 2007

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Using 51 V magic angle spinning solid-state NMR, SSNMR, spectroscopy and quantum chemical DFT calculations we have characterized the chemical shift and quadrupolar coupling parameters of a series of 8 hydroxylamido vanadium(V) dipicolinate complexes of the general formula VO(dipic)(ONR 1 R 2 )(H 2 O) where R 1 and R 2 can be H, CH 3 , or CH 2 CH 3 . This class of vanadium compounds was chosen for investigation because of their seven coordinate vanadium atom, a geometry for which there is limited 51 V SSNMR data. Furthermore, a systematic series of compounds with different electronic properties are available and allows for the effects of ligand substitution on the NMR parameters to be studied. The quadrupolar coupling constants, C Q , are small, 3.0 to 3.9 MHz, but exhibit variations as a function of the ligand substitution. The chemical shift tensors in the solid state are sensitive to changes in both the hydroxylamide substituent and the dipic ligand, a sensitivity which is not observed for isotropic chemical shifts in solution. The chemical shift tensors span approximately 1000 ppm, and are nearly axially symmetric. Based on DFT calculations of the chemical shift tensors, one of the largest contributors to the magnetic shielding anisotropy is an occupied molecular orbital with significant vanadium d z 2 character along the V=O bond.

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“…This is consistent with the predicted limitation of this method to QCC values of 4 MHz or less. 23 On the basis of the electric field gradient calculations, 9 an increase of the coordination number of a sodium cation at SII would decrease the quadrupole coupling constant of 23 Na. 24 This prediction has been confirmed experimentally for the interaction with meta-xylene molecules, 25 and as will be shown below by a combination of 23 Na MAS and DOR NMR experiments, it will hold true for Mo(CO) 6 in a deeper analysis of the experiment displayed in Figure 3d.…”

Section: Resultsmentioning

confidence: 99%

“…Another line with a Gaussian/Lorentzian shape centered at -26 ppm (B 0 ) 9.4 T) has been observed for partially rehydrated Na + cations (component D). These assignments were derived by calculations of electric field gradients for the different sites with a point charge model 9 and by ion exchanged samples. 10 For a cesium-exchanged zeolite Y, the results from NMR are confirmed by a Rietveld refinement.…”

Section: Introductionmentioning

confidence: 99%

¹³C and ²³Na Solid-State NMR Study on Zeolite Y Loaded with Mo(CO)₆

et al. 1997

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The 23 Na MAS and double rotation (DOR) NMR spectra of dehydrated zeolite NaY loaded with two molecules of Mo(CO) 6 per supercage show three components distinguished by the corresponding quadrupole coupling constants (QCC). Sodium cations in the hexagonal prisms (SI sites) are characterized by a narrow Gaussian line with a QCC value close to zero. A second component with quadrupole coupling constants between 4.4 and 4.8 MHz is assigned to Na + cations located in the sodalite cages, and the third component with QCC ranging between 2.2 and 2.8 MHz is due to sodium cations in the supercages interacting with Mo(CO) 6 . These sites are characterized by structural and/or dynamical disorder as observed by typical line shape properties. Adsorption of Mo(CO) 6 in Y zeolites, where all Na + cations in the supercages of NaY have been exchanged with NH 4 + or H + , causes the sodium cations in the sodalite cages to migrate into the supercages in order to interact with the adsorbent. For the NH 4 + -exchanged sample, the anisotropic chemical shift parameters for 13 C in Mo(CO) 6 have been analyzed at ambient temperature. From the results a fast anisotropic local reorientation of Mo(CO) 6 follows. The rotation is about a 3-fold axis of the octahedral complex. The octahedron is slightly elongated along the rotation axis by about 4°when it is located close to the sodium cations.

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23Na NMR Spectroscopy of Solids: Interpretation of Quadrupole Interaction Parameters and Chemical Shifts

Cited by 285 publications

References 7 publications

A study on hydration behaviors of interlayer cations in montmorillonite by solid state NMR

A study on hydration behaviors of interlayer cations in montmorillonite by solid state NMR

Investigating the Vanadium Environments in Hydroxylamido V(V) Dipicolinate Complexes Using ⁵¹V NMR Spectroscopy and Density Functional Theory

¹³C and ²³Na Solid-State NMR Study on Zeolite Y Loaded with Mo(CO)₆

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23Na NMR Spectroscopy of Solids: Interpretation of Quadrupole Interaction Parameters and Chemical Shifts

Cited by 285 publications

References 7 publications

A study on hydration behaviors of interlayer cations in montmorillonite by solid state NMR

A study on hydration behaviors of interlayer cations in montmorillonite by solid state NMR

Investigating the Vanadium Environments in Hydroxylamido V(V) Dipicolinate Complexes Using 51V NMR Spectroscopy and Density Functional Theory

13C and 23Na Solid-State NMR Study on Zeolite Y Loaded with Mo(CO)6

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Investigating the Vanadium Environments in Hydroxylamido V(V) Dipicolinate Complexes Using ⁵¹V NMR Spectroscopy and Density Functional Theory

¹³C and ²³Na Solid-State NMR Study on Zeolite Y Loaded with Mo(CO)₆