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Author: Andre Sutrisno Publisher: ISBN: Category : Languages : en Pages :
Book Description
Preparation and characterization of inorganic materials is a crucial practice because understanding the relationship between structure and property is important for improving current performance and developing novel materials. Many metal centers in technologically and industrially important materials are unreceptive low- quadrupolar nuclei (i.e., possessing low natural abundance, low NMR frequencies and large quadrupole moments) and they usually give rise to very broad NMR resonances and low signal-to-noise ratios, making it difficult to acquire their solid-state NMR spectra. This thesis focuses on the characterization of inorganic materials using solid-state NMR (SSNMR) spectroscopy at very high magnetic field of 21.1 T in combination with quantum chemical calculations for computational modeling. In the first part of this thesis, 67Zn and 17O SSNMR studies of several microporous materials were reported. The results of 67Zn SSNMR studies from several important metal-organic frameworks (MOFs), in particular, zeolitic imidazolate frameworks (ZIFs) were presented. 67Zn SSNMR spectroscopy was used to gain structural information regarding the desolvation process in MOF-5. Furthermore, 67Zn SSNMR spectroscopy were utilized to study the host-guest interactions in ZIF-8 loaded with different guest molecules. Static 67Zn SSNMR spectra of microporous zinc phosphites (ZnP) and zinc phosphates (ZnPO) were also acquired at natural abundance. The Gaussian calculation results on a model cluster for ZnP indicate that Zn-O bond length is the most dominant factor to the observed quadrupolar coupling constant (CQ) among other geometric parameters around Zn centres. The local structures of the framework oxygen sites in molecular sieve SAPO-34 were directly probed by several 17O SSNMR techniques. The involvement of water vapor during the SAPO-34 formation in dry-gel conversion (DGC) synthesis was also investigated. In the second part, 91Zr and 33S SSNMR spectra of layered zirconium phosphates (ZrP) and transition metal disulfides (MS2) were obtained. The empirical correlations between NMR parameters and various structural parameters were used for obtaining partial structural information in Li+ and Co(NH3)63+ exchanged layered ZrP. For a series of closely related MS2 materials, the observed differences in the CQ(33S) values were rationalized by considering the difference in their geometrical arrangements. The final part of this thesis featured two examples of SSNMR spectroscopy of exotic nuclei in some interesting inorganic materials. (i) The experimental 135/137Ba SSNMR spectroscopy and theoretical studies of -BBO, an important non-linear optical (NLO) material, indicate that the true crystal structure of -BBO is R3c space group rather than R3. (ii) An ultrahigh field natural abundance 73Ge SSNMR study of two representative germanium containing materials [GeCl2-dioxane and GePh4] demonstrated that acquiring 73Ge wideline NMR spectra of germanium compounds where the Ge experiences an extremely large quadrupolar interaction is feasible and that the small 73Ge chemical shielding anisotropy (CSA) can be directly measured.
Author: Andre Sutrisno Publisher: ISBN: Category : Languages : en Pages :
Book Description
Preparation and characterization of inorganic materials is a crucial practice because understanding the relationship between structure and property is important for improving current performance and developing novel materials. Many metal centers in technologically and industrially important materials are unreceptive low- quadrupolar nuclei (i.e., possessing low natural abundance, low NMR frequencies and large quadrupole moments) and they usually give rise to very broad NMR resonances and low signal-to-noise ratios, making it difficult to acquire their solid-state NMR spectra. This thesis focuses on the characterization of inorganic materials using solid-state NMR (SSNMR) spectroscopy at very high magnetic field of 21.1 T in combination with quantum chemical calculations for computational modeling. In the first part of this thesis, 67Zn and 17O SSNMR studies of several microporous materials were reported. The results of 67Zn SSNMR studies from several important metal-organic frameworks (MOFs), in particular, zeolitic imidazolate frameworks (ZIFs) were presented. 67Zn SSNMR spectroscopy was used to gain structural information regarding the desolvation process in MOF-5. Furthermore, 67Zn SSNMR spectroscopy were utilized to study the host-guest interactions in ZIF-8 loaded with different guest molecules. Static 67Zn SSNMR spectra of microporous zinc phosphites (ZnP) and zinc phosphates (ZnPO) were also acquired at natural abundance. The Gaussian calculation results on a model cluster for ZnP indicate that Zn-O bond length is the most dominant factor to the observed quadrupolar coupling constant (CQ) among other geometric parameters around Zn centres. The local structures of the framework oxygen sites in molecular sieve SAPO-34 were directly probed by several 17O SSNMR techniques. The involvement of water vapor during the SAPO-34 formation in dry-gel conversion (DGC) synthesis was also investigated. In the second part, 91Zr and 33S SSNMR spectra of layered zirconium phosphates (ZrP) and transition metal disulfides (MS2) were obtained. The empirical correlations between NMR parameters and various structural parameters were used for obtaining partial structural information in Li+ and Co(NH3)63+ exchanged layered ZrP. For a series of closely related MS2 materials, the observed differences in the CQ(33S) values were rationalized by considering the difference in their geometrical arrangements. The final part of this thesis featured two examples of SSNMR spectroscopy of exotic nuclei in some interesting inorganic materials. (i) The experimental 135/137Ba SSNMR spectroscopy and theoretical studies of -BBO, an important non-linear optical (NLO) material, indicate that the true crystal structure of -BBO is R3c space group rather than R3. (ii) An ultrahigh field natural abundance 73Ge SSNMR study of two representative germanium containing materials [GeCl2-dioxane and GePh4] demonstrated that acquiring 73Ge wideline NMR spectra of germanium compounds where the Ge experiences an extremely large quadrupolar interaction is feasible and that the small 73Ge chemical shielding anisotropy (CSA) can be directly measured.
Author: Kevin Burgess Publisher: ISBN: Category : University of Ottawa theses Languages : en Pages :
Book Description
In the past decade, the field of NMR spectroscopy has seen the emergence of ever more powerful superconducting magnets, which has opened the door for the observation of many traditionally challenging or non-receptive nuclei. In this dissertation, a variety of ionic solids with organic coordination environments are investigated using quadrupolar solid-state NMR experiments with an ultrahigh-field magnet (21.1 T). Two general research directions are presented including a 79/81Br solid-state NMR study of a series of 6 triphenylphosphonium bromides for which single-crystal X-ray structures are reported herein. A second research direction is also presented wherein alkaline-earth metal (25Mg, 43Ca, and 87Sr) solid-state NMR is used to characterize a systematic series of 16 aryl and alkyl carboxylates. In both studies, the quadrupolar nuclei studied are deemed zexoticy due to their unreceptive nature to NMR spectroscopic analysis including low natural abundances, large quadrupole moments, or low resonance frequencies. A variety of coordination modes to alkaline-earth metals, including N-atom coordination, are characterized herein for the first time using alkaline-earth metal solid-state NMR. In all cases, the electric field gradient (EFG) and chemical shift (CS) tensors are characterized and correlated to structural features such as interatomic distances measured from the crystal structure of the compound under study. In all of the projects undertaken herein, the gauge-including projector-augmented-wave density functional theory (GIPAW DFT) method is used, which allows for the prediction and rationalization of the experimental EFG and CS tensor parameters based on the input crystal structure. In the case of 43Ca solid-state NMR experiments reported in this dissertation, a linear correlation between the calculated and experimental 43Ca quadrupolar coupling constants, CQ, is used as a calibration curve for GIPAW DFT calculations performed on the 18 structural models currently available for the vaterite polymorph of CaCO3. Vaterite cannot be fully characterized by X-ray diffraction alone; therefore an NMR crystallography protocol is used in order to identify the model that best accounts for 43Ca solid-state NMR experiments performed on vaterite. It is expected that the conclusions from this dissertation can be used for future studies involving structural refinement and elucidation of solid materials containing challenging quadrupolar nuclei.
Author: Roshanak Teymoori Publisher: ISBN: Category : Nuclear magnetic resonance Languages : en Pages : 276
Book Description
This thesis is concerned with applications of modern solid-state NMR spectroscopy. Investigations of three quadrupolar nuclei (51V, 17O, and 23Na) are undertaken to demonstrate the practicality of solid-state nuclear magnetic resonance, SSNMR in studies of compounds containing these nuclei. The goal of each project is to gain insight into the effect of the local environment on the NMR observables. Vanadium-51 solid-state NMR has been used to study oxo- and peroxo-vanadium compounds. The 51V nucleus is examined to determine the vanadium magnetic shielding, MS and electric field gradient, EFG tensors. Density functional theory, DFT, has been utilized to calculate MS and EFG tensors to corroborate experimental data and to provide insight into the relationship between molecular and electronic structure. In addition the hyperbolic secant, HS pulse sequence has been used to provide spectra from which information about the shielding anisotropy of [V(O)(ONMe2)2]2O could be gained. An investigation of oxygen-17 solid-state NMR studies of ligand, 17OP(p-Anis)3 and complex of InI3[17OP(p-Anis)3]2 powder samples has also been carried out. Coordination of oxygen to indium causes a change in the 17O chemical shift tensor. DFT calculations are also utilized and the theoretical results are compared with the corresponding experimental values. Finally, solid-state sodium-23 NMR investigations of series of sodium salts, (sodium nitroprusside dihydrate, sodium bromate, sodium chlorate, sodium nitrate, sodium nitrite, sodium selenite and anhydrous disodium hydrogen phosphate) were carried out to determine 23Na MS and EFG tensor parameters. The CASTEP and BAND codes were employed to calculate the EFG and MS tensors. In addition, in the case of sodium nitroprusside solid-state 17O and 15N NMR studies, as well as computational investigations of the corresponding EFG and MS tensors, were undertaken. This Thesis reported the first experimental demonstration of sodium CS tensors determined from solid-state NMR spectroscopy of powder samples of these sodium salts. It also demonstrated the use of first-principles calculations, based on DFT theory in the CASTEP and BAND codes, to investigate the 23Na EFG and MS tensors for these sodium salts.
Author: Jerry C. C. Chan Publisher: Springer ISBN: 3642248039 Category : Science Languages : en Pages : 328
Book Description
Dipolar Recoupling, by Niels Chr. Nielsen, Lasse A. Strassø and Anders B. Nielsen.- Solid-State NMR Techniques for the Structural Determination of Amyloid Fibrils, by Jerry C. C. Chan.- Solid-State 19F-NMR of Peptides in Native Membranes, by Katja Koch, Sergii Afonin, Marco Ieronimo, Marina Berditsch and Anne S. Ulrich.- Probing Quadrupolar Nuclei by Solid-State NMR Spectroscopy: Recent Advances, by Christian Fernandez and Marek Pruski.- Solid State NMR of Porous Materials Zeolites and Related Materials, by Hubert Koller and Mark Weiß.- Solid-State NMR of Inorganic Semiconductors, by James P. Yesinowski.-
Author: Oc Hee Han Publisher: ISBN: Category : Languages : en Pages : 254
Book Description
The general purpose of my research in this thesis is to apply solid state NMR of quadrupole nuclei to characterize and probe the chemical, structural, physical and electronic properties of materials, such as group III-V semiconductors, AlCl$sb3cdot$THF complexes, graphite intercalated with AlCl$sb3$ (and related systems), and the copper-free high T$sb{rm c}$ superconductor (Ba$sb{0.6}$K$sb{0.4}$BiO$sb3$), and related systems. Overall, I have tried to use solid-state NMR to give new information about structure in a variet of interesting and important conducting compounds, especially: semiconductors, superconductors, and metallic intercalation compounds (together with additional studies on appropriate "model" compounds).
Author: Andre Sutrisno
Author: Andre Sutrisno
Author: Kevin Burgess
Author: Hye Kyung Cho Timken
Author: Roshanak Teymoori
Author: Robert Alan Kinsey
Author: Jerry C. C. Chan
Author: 
Author: Thomas J. N. Hooper
Author: Davis Sherman Rovnyak
Author: Oc Hee Han