29Si Chemical Shifts Research Articles

Unmasking Fluorinated Moieties on the Surface of Hydride-Terminated Silicon Nanoparticles.

Despite the widespread use of hydrofluoric acid (HF) in the preparation of silicon surfaces, the true nature of fluorinated surface species remains unclear. Here, we employ an array of characterization techniques led by solid-state nuclear magnetic resonance spectroscopy to uncover the nature of fluorinated moieties on the surface of hydride-terminated silicon nanoparticles (H-SiNPs). A structural model that explains the observed trends in 19F and 29Si magnetic shielding is proposed and further supported by quantum chemical computations. Fluorine is incorporated into local oxidation domains on the surface and clustered at the interface of the oxide and surrounding hydride-terminated surface. Silicon sites capped by a single fluorine are also identified by their distinct 19F and 29Si chemical shifts, providing insight into how fluorine termination influences the electronic structure. The extent of fluorine passivation and the effects of fluorine on the optical properties of SiNPs are also discussed. Finally, challenges associated with Teflon contamination are highlighted that future explorations of nanomaterials may have to contend with.

Potassium Hexamethyldisilazide (KHMDS): Solvent-Dependent Solution Structures.

Solution structures of potassium hexamethyldisilazide [KHMDS] and labeled [15N]KHMDS were examined using a number of analytical methods including 29Si NMR spectroscopy and density functional theory computations. A combination of 15N-29Si couplings, 29Si chemical shifts, and the method of continuous variations reveals dimers, monomers, and ion pairs. Weakly coordinating monofunctional ligands such as toluene, N,N-dimethylethylamine, and Et3N afford exclusively dimers. 1,3-Dioxolane, THF, dimethoxyethane, hexamethylphosphoramide, and diglyme provide dimers at low ligand concentrations and monomers at high ligand concentrations. N,N,N',N'-Tetramethylethylenediamine and N,N,N',N'-tetramethylcyclohexanediamine provide exclusively dimers at all ligand concentrations at ambient temperatures and significant monomer at -80 °C. Studies of 12-crown-4 ran into technical problems. Equimolar 15-crown-5 forms a dimer, whereas excess 15-crown-5 affords a putative ion pair. Whereas equimolar 18-crown-6 also affords a dimer, an excess provides a monomer rather than a solvent-separated ion pair. [2.2.2]cryptand affords what is believed to be a contact-ion-paired cryptate. Solvation was probed using largely density functional theory (DFT) computations. Thermally corrected energies are consistent with lower aggregates and higher solvates at low temperatures, but the magnitudes of the computed temperature dependencies were substantially larger than the experimentally derived data.

Densification of sodium and magnesium aluminosilicate glasses at ambient temperature: structural investigations by solid-state nuclear magnetic resonance and molecular dynamics simulations.

Sodium and magnesium aluminosilicate glasses with compositions 20Na2O-20Al2O3-60SiO2 (NAS) and 20MgO-20Al2O3-60SiO2 (MAS) were subjected to a 12 and 25 GPa compression and decompression at room temperature, resulting in density increases from 3.7% to 5.3% (NAS) and from 8.2 to 8.4% (MAS), respectively. The pressurization at 25 GPa was done on 17O-enriched glasses, to facilitate characterization by 17O NMR. The structural changes associated with this process have been investigated by solid state 29Si, 27Al, 23Na, 25Mg, and 17O magic-angle spinning NMR and compared with the situation in thermally relaxed glasses and/or glasses prepared at ambient pressure. While in the Na aluminosilicate glass only subtle structural changes were observed in a sample densified at 12 GPa, the average coordination number of Al 〈CN(Al)〉 increases moderately from 4.00 to 4.26 by pressurization at 25 GPa. In the Mg-based system, 〈CN(Al)〉 increases from 4.34 to 4.57 to 4.83 in the sequence 10-4 GPa → 12 GPa → 25 GPa. The experimental result at 25 GPa was qualitatively confirmed by molecular dynamics (MD) simulations. Overall, pressurization results in more positive 29Si and 17O chemical shifts, most likely reflecting a reduction in the Si-O-Si and Si-O-Al bonding angles in the pressurized glasses. Furthermore, the results are also consistent with either an increased number of non-bridging O-atoms upon pressurization, or a larger number of Si-O-Al or Al-O-Al linkages. The significantly higher sensitivity of MAS, compared to NAS glass, to an increase in 〈CN(Al)〉 upon pressurization, provides a good structural rationale for its significantly higher crack initiation resistance.

The Hexacoordinate Si Complex SiCl4(4-Azidopyridine)2—Crystallographic Characterization of Two Conformers and Probing the Influence of SiCl4-Complexation on a Click Reaction with Phenylacetylene

4-Azidopyridine (1) and SiCl4 react with the formation of the hexacoordinate silicon complex SiCl4(4-azidopyridine)2 (2). Upon dissolving in warm chloroform, the complex dissociates into the constituents 1 and SiCl4 and forms back upon cooling. Depending on the cooling, two different crystalline modifications of 2 were obtained, which feature two different trans-conformers. Slow cooling to room temperature afforded conformer 2′, which features coplanar pyridine rings. Rapid cooling to −39 °C afforded crystals of conformer 2″, in which the planes of the pyridine ligands are nearly orthogonal to one another. Whereas 2′ resembles the molecular arrangement of various other known SiX4(pyridine)2 (X = halide) complexes, 2″ represents the first crystallographically confirmed example of a SiX4(pyridine)2 complex in this conformation. Conformers 2′ and 2″ were studied with 13C and 29Si solid state NMR spectroscopy. Their differences in 29Si chemical shift anisotropy, as well as energetic differences, were further investigated with computational analyses. In spite of the similar stabilities of the two conformers as isolated molecules, the crystal packing of 2″ is less stable, and its crystallization is interpreted as a kinetically controlled effect of seed formation. (3+2)-cycloaddition of 1 and phenylacetylene in toluene at 110 °C yields a mixture of 1-(4-pyridyl)-4-phenyl-1,2,3-triazole (1,4-3) and 1-(4-pyridyl)-5-phenyl-1,2,3-triazole (1,5-3) in approximate 1:2 molar ratio. The crystal structures of the two isomers were determined via X-ray diffraction. In chloroform (at 60 °C), this reaction is slow (less than 2% conversion within 4 h), but the presence of SiCl4 enhanced the rate of the reaction slightly, and it shifted the triazole isomer ratio to ca. 1:6 in favor of 1,5-3.

Local Geometry of Tetrahedrally Coordinated Boron Correlates with 11B NMR Chemical Shifts in Borosilicate Minerals

Chemical shifts from the 11B nuclear magnetic resonance (NMR) spectra of crystalline borosilicate minerals with highly ordered, tetrahedrally coordinated boron atoms (B) linearly correlate with the local geometric parameters related to the B–O–T angles (T denotes a tetrahedrally coordinated atom) obtained from single-crystal X-ray diffraction. The correlations between the 11B NMR chemical shifts and structural parameters are similar in functional form to the well-known correlations of 29Si and 27Al NMR chemical shifts with structural features of silicates and aluminosilicates, respectively. These correlations enable the use of 11B NMR chemical shifts to elucidate the local geometry of tetrahedrally coordinated B and aid in establishing B ordering among the crystallographic T-sites within crystalline borosilicates.

Machine Learning Full NMR Chemical Shift Tensors of Silicon Oxides with Equivariant Graph Neural Networks.

The nuclear magnetic resonance (NMR) chemical shift tensor is a highly sensitive probe of the electronic structure of an atom and furthermore its local structure. Recently, machine learning has been applied to NMR in the prediction of isotropic chemical shifts from a structure. Current machine learning models, however, often ignore the full chemical shift tensor for the easier-to-predict isotropic chemical shift, effectively ignoring a multitude of structural information available in the NMR chemical shift tensor. Here we use an equivariant graph neural network (GNN) to predict full 29Si chemical shift tensors in silicate materials. The equivariant GNN model predicts full tensors to a mean absolute error of 1.05 ppm and is able to accurately determine the magnitude, anisotropy, and tensor orientation in a diverse set of silicon oxide local structures. When compared with other models, the equivariant GNN model outperforms the state-of-the-art machine learning models by 53%. The equivariant GNN model also outperforms historic analytical models by 57% for isotropic chemical shift and 91% for anisotropy. The software is available as a simple-to-use open-source repository, allowing similar models to be created and trained with ease.

A theoretical study of dynamic processes observed in trimethylsilyl-1H-pyrazoles: prototropy and silylotropy

The 1H, 13C, 15N and 29Si chemical shifts of three trimethylsilyl-1H-pyrazoles were calculated and compared with literature results; the calculations were carried out at the GIAO/B3LYP/6–311 + + G(d,p) level resulting in a very good agreement that allows to predict with confidence the missing experimental values. The prototropic barrier of 4-trimethylsilyl-1H-pyrazole (1) as well as the silylotropic barriers of 1-trimethylsilyl-1H-pyrazole (2) and 1-trimethylsilyl-4-methyl-1H-pyrazole (3) were also calculated and the mechanism was established, the accordance with the experimental values being satisfactory.

Silica incorporation into sodium aluminum phosphate glasses: Structural characterization by Raman spectroscopy and multinuclear solid-state NMR

Optical fiber glasses in the system (59-xP2O5)-xSiO2–13Al2O3-28Na2O show non-linear trends in the glass-transition temperatures, thermal expansion coefficients, and weathering stabilities. The structural origins have been studied using solid-state NMR and Raman spectroscopies on a series of bulk glasses with 0 ≤ x ≤ 13. Two types of P2 units – those dominantly interacting with Na+and those interacting more strongly with Al can be differentiated by 31P{23Na} and 31P{27Al} double resonance experiments. Silicon is four-coordinated, fully polymerized, and engaged in Si-O-P linkages. Trends in the 29Si chemical shifts and the 31P-31P dipolar interaction strengths are related to the Si-O-P, Si-O-Al, and P-O-P connectivity distributions, providing a rationale for changes in macroscopic properties.

Lead silicate glass structure: New insights from diffraction and modeling of probable lone pair locations

AbstractStructures of binary PbO‐SiO2 glasses have been studied in detail over the compositional range 35 to 80 mol% PbO using high‐resolution neutron diffraction, high‐energy X‐ray diffraction, static 207Pb NMR, and structural modeling. The changes in the local environment of Pb(II) are subtle; it has a low coordination to oxygen (∼3 to 4) plus a stereochemically active electron lone pair and, thus, behaves as a glass network forming (or intermediate) cation over the entire composition range. This conclusion contradicts previous reports that Pb(II) is a network modifier at low concentrations, and is supported by an analysis of lead and alkaline earth silicate glass molar volumes. The Pb‐O peak bond length shortens by 0.04 Å with increasing PbO content, indicating stronger, more covalent bonding, and consistent with an increase in the number of short (≤ 2.70 Å) Pb‐O bonds, from 3.3 to 3.6. This is accompanied by increased axial symmetry of the Pb(II) sites, and is interpreted as a gradual transition toward square pyramidal [PbO4] sites such as those found in crystalline PbO polymorphs. An attendant decrease in the periodicity associated with the first sharp diffraction peak (FSDP) toward that of β‐PbO, accompanied by increases in the correlation lengths associated with the plumbite network (FSDP) and silicate anions (neutron prepeak), provides evidence of increased intermediate‐range order and has implications for the glass forming limit imposed by crystallization. Pb(II) electron lone pairs occupy the natural voids within the silicate network at low PbO contents, while at high PbO contents they aggregate to create voids that form part of the plumbite network, analogous to the open channels in Pb11Si3O17 and the layered structures of α‐ and β‐PbO. Si‐O and Pb‐O bond lengths have been correlated with 29Si and 207Pb NMR chemical shifts, respectively. This is the first time that such correlations have been demonstrated for glasses and attests to the accuracy with which pulsed neutron total scattering can measure average bond lengths.

Solid State NMR Analysis for Hide Powder Tanned by Aluminum, Silicon and Phosphorus Tanning Agents before and after Hydrothermal Denaturation

In order to investigate the change of chemical bonds between tanning agents and collagen molecules directly, hide powder tanned by aluminum, silicon and phosphorus tanning agents were prepared. The chemical shifts of Al, Si and P in tanned hide powder were analyzed by solid-state 27Al NMR, 29Si NMR and 31P NMR. The results showed that, the chemical shift of Al in aluminum tanned hide powder which interacted with collagen molecules through coordination bond could be regarded as unchanging after hydrothermal denaturation (only slightly moved to high field area). The chemical shift of Si in silicon tanned hide powder which interacted with collagen molecules through hydrogen bond did not change after hydrothermal denaturation. The chemical shift of P in phosphorus tanned hide powder, which interacted with collagen molecules through covalent bond, was obviously shifted to the high field area after hydrothermal denaturation.

Anomalous magnetism of uranium(IV)-oxo and -imido complexes reveals unusual doubly degenerate electronic ground states

Anomalous magnetism of uranium(IV)-oxo and -imido complexes reveals unusual doubly degenerate electronic ground states

Structure‐property relations in crack‐resistant alkaline‐earth aluminoborosilicate glasses studied by solid state NMR

AbstractThe effect of the average ionic potential ξ = Ze/r of the network modifier cations on crack initiation resistance (CR) and Young's modulus E has been measured for a series of alkaline‐earth aluminoborosilicate glasses with the compositions 60SiO2–10Al2O3–10B2O3–(20−x)M(2)O–xM’O (0 ≤ x ≤ 20; M, M’ = Mg, Ca, Sr, Ba, Na). Systematic trends indicating an increase of CR with increasing ionic potential, ξ, have been correlated with structural properties deduced from the NMR interaction parameters in 29Si, 27Al, 23Na, and 11B solid state NMR. 27Al NMR spectra indicate that the aluminum atoms in these glasses are essentially all four‐coordinated, however, the average quadrupolar coupling constant <CQ> extracted from lineshape analysis increases linearly with increasing average ion potential computed from the cation composition. A similar linear correlation is observed for the average 29Si chemical shift, whereas the fraction of four‐coordinate boron decreases linearly with increasing ξ. Altogether the results indicate that in pure alkaline‐earth boroaluminosilicate glasses the crack resistance/E‐modulus trade‐off can be tailored by the alkaline‐earth oxide inventory. In contrast, the situation looks more complicated in glasses containing both Na2O and the alkaline‐earth oxides MgO, CaO, SrO, and BaO. For 60SiO2–10Al2O3–10B2O3–10MgO–10Na2O glass, the NMR parameters, interpreted in the context of their correlations with ionic potentials, are consistent with a partial network former role of the MgO component, enhancing crack resistance. Altogether the presence of MgO in aluminoborosilicate glasses helps overcome the trade‐off issue between high crack resistance and high elasticity modulus present in borosilicate glasses, thereby offering additional opportunities for the design of glasses that are both very rigid and very crack resistant.

Progress in the preparation and characterization of silylene iron, cobalt and nickel complexes.

The synthesis and characterization of Fe, Co and Ni complexes supported by silylene ligands in the past ten years are summarized. Due to the decrease of the electron cloud density on the Si atom after coordination, the downfield shift of the 29Si chemical shift is accompanied by the coordination between the free silylene ligand and metal. The strong electron-donating ability of silylene makes the metal center more electron-rich, which is conducive to the oxidative addition reaction in the metal center. In some cases, the coordination ability of silylene is stronger than those of phosphine and carbene ligands. Therefore, silylene transition metal complexes have better catalytic activity. The further challenges in this field are to develop new polydentate silylene ligands, synthesize chelate silylene-phosphine and silylene-carbene ligands, and design new silylene transition metal complexes for more catalytic research.

Experimental and theoretical study of deactivated HDT catalysts by Si species deposited on their surfaces: Models proposition, structural and thermodynamic analysis

It is known that silicon species originate from the thermal degradation of the polydimethylsiloxane, adsorb on the catalysts surface used for hydrotreatment in the oil refining industry. This severely affects the performance of these catalysts and considerably reduce their lifetime. Combining 29Si and 13C CP/MAS NMR experiments and DFT calculations, we investigated the poisoning process of these catalysts by silicon species in order to obtain a better understanding of this process. Two structural models (mono and bilayer) for amorphous silica deposited on the γ-Al2O3 surface and some intermediates that can be formed during this process were proposed. From the calculated 29Si chemical shifts, it was possible to identify chemical shifts variations due to different structural elements for each species, thereby, it was possible to make a more appropriate assignment of the resonances found in 29Si CP/MAS NMR spectra in the literature. Besides that, through of the good agreements obtained between the experimental and simulated 29Si CP/MAS NMR spectra, we identified that probably the D4, T1, T3, T4, Q1 and Q2 species are present in the initial stage of the contamination and that the amorphous silica bilayer model deposited on the γ-Al2O3 surface best characterizes the final stage of the contamination. Moreover, the thermodynamic analysis revealed that the chemisorption reaction of the Hexamethylcyclotrisiloxane (D3) compound is much more stable than the Octamethylcyclotetrasiloxane (D4) compound and of a fragment (corresponding to 13 or 14 of the D3 and D4compounds, respectively), and the chemisorption reaction of the fragment presented the highest values of ΔG°. This leads us to deduce that the D3 and D4 compounds chemisorb preferentially without breaking. Besides, it also showed that the amorphous silica formation process on the γ-Al2O3 surface is spontaneous and the bilayer formation reaction is more stable than the monolayer.

Sodium Hexamethyldisilazide: Using 15N-29Si Scalar Coupling to Determine Aggregation and Solvation States.

29Si NMR spectroscopy, the method of continuous variations, and density functional theory computations show that sodium hexamethyldisilazide (NaHMDS) is a disolvated dimer in toluene, a mixture of disolvated dimer and tetrasolvated monomer in THF/toluene, and exclusively monomer in neat THF. The dioxane-solvated NaHMDS only partially deaggregates to monomer even in neat dioxane. 15N-29Si coupling constants and 29Si chemical shifts show a high and dependable correlation with the aggregation state. Monitoring either chemical shift or coupling constant versus THF concentration even in the high-temperature, rapid-exchange limit affords the solvation numbers consistent with DFT computations. The preparation of 15N-labeled NaHMDS has been improved.

Solid-state 29Si NMR spectra of pure silica zeolites for the International Zeolite Association Database of Zeolite Structures

Abstract With a view to extending the comprehensiveness of the International Zeolite Association Database of Zeolite Structures, this paper reports initial efforts to incorporate solid-state nuclear magnetic resonance (NMR) spectra in the database. A collection of 51 29Si solid-state NMR spectra of pure silica zeolites with 39 different framework types, gleaned from the published scientific literature over the past four decades, is presented here. High resolution 29Si solid-state NMR spectra showing crystallographic resolution of the Si sites were collected, digitized, analyzed, and incorporated into the online Database of Zeolite Structures and can be freely viewed online in an interactive fashion. In addition, with such a large dataset of 29Si solid-state NMR spectra, various correlations between 29Si chemical shifts and geometric parameters describing the local structure around the Si sites were evaluated, showing that the best correlation results when both Si–O–Si bond angles and Si–O bond lengths are considered. It is anticipated that this addition of solid-state NMR spectra to the Database of Zeolite Structures will be of great interest and usefulness to the international community of zeolite scientists.

Weak Interactions Get Strong: Synergy between Tetrel and Alkaline-Earth Bonds.

Weak and strong noncovalent interactions such as tetrel bonds and alkaline-earth bonds, respectively, cooperate and get reinforced when acting together in ternary complexes of general formula RN··· SiH3F···MY, where MY is a Be or Mg derivative and RN is a N-containing Lewis base with different hybridization patterns. Cooperativity has been studied in the optimized MP2/aug'-cc-pVTZ ternary complexes by looking at changes on geometries, binding energies, 29Si NMR chemical shifts, and topological features according to the atoms in molecules theoretical framework. Our study shows that cooperativity in terms of energy is in general significant: more than 40 kJ/mol, and up to 83.6 kJ/mol in the most favorable case. The weakest the isolated interaction, the strongest the reinforcement in the ternary complex; in this sense, the tetrel bond is shortened enormously, between 0.3 and 0.6 Å. This dramatic reinforcement of the tetrel bond is also nicely reflected in the positive variations of the 29Si chemical shifts in all the ternary complexes. At the same time the ternary complexes are characterized by the presence of totally planar silyl group, due to the pentacoordination of the Si atom. Both the hybridization of the N base and the geometry imposed by the alkaline-earth ligands have a strong influence on the binding energies, as they modify the donor ability of N and the Lewis acid character of the alkaline-earth metal.

Modelling the Effect of Zero-Field Splitting on the 1H, 13C and 29Si Chemical Shifts of Lanthanide and Actinide Compounds

The prediction of paramagnetic NMR (pNMR) chemical shifts in molecules containing heavy atoms presents a significant challenge to computational quantum chemistry. The importance of meeting this challenge lies in the central role that NMR plays in the structural characterisation of chemical systems. Hence there is a need for reliable assignment and prediction of chemical shifts. In a previous study [Trends in Physical Chemistry, 17, 25–57, (2017)] we looked at the computation of pNMR chemical shifts in lanthanide and actinide complexes using a spin Hamiltonian approach. In that study we were principally concerned with molecules with S = 1/2 ground states. In the present work we extend that study by looking at the effect of zero field splitting (ZFS) for six complexes with S = 3/2 ground states. It is shown that the inclusion of ZFS can produce substantial shifts in the predicted chemical shifts. The computations presented are typically sufficient to enable assignment of experimental spectra. However for one case, in which the peaks are closely clustered, the inclusion of ZFS re-orders the chemical shifts making assignment quite difficult. We also observe, and echo, the previously reported importance of including the paramagnetic spin-orbit hyperfine interaction for 13 C and 29 Si atoms, when these are directly bound to a heavy element and thus subject to heavy-atom-light-atom effects. The necessary computations are very demanding, and more work is needed to find theoretical and computational approaches that simplify the evaluation of this term. We discuss the computation of each term required in the spin Hamiltonian. The systems we study in this work are restricted to a single heavy atom ion (one Nd(III) and five U(III) complexes), but typify some of the computational complexity encountered in lanthanide and actinide containing molecules.

Structure of P2O5–SiO2 Pure Network Former Glasses Studied by Solid State NMR Spectroscopy

The structure of binary (SiO2)100-x–(P2O5)x glasses has been investigated by Raman scattering, 29Si and 31P magic angle spinning (MAS) as well as static 31P NMR spectroscopy. 29Si chemical shift trends reflect the successive replacement of Si–O–Si by Si–O–P linkages as the compositional parameter x is increased. While 31P MAS NMR does not resolve separate phosphate species, the static 31P NMR lineshapes were successfully simulated by considering the effect of uncorrelated distribution functions of the chemical shift tensor components upon the line shape. On the basis of these simulations, which were also found to be consistent with the experimental 31P MAS NMR spectra, two distinct sites can be resolved: a dominant site characterized by an axially symmetric chemical shift tensor, assigned to P(3) units, and (only in the case of the x = 25 and 30 glasses) a Gaussian component reflecting phosphate species interacting with five- and six-coordinated silicon species. For 0 ≤ x < 25, the decrease in average coo...

Effect of Ge/Si substitutions on the local geometry of Si framework sites in zeolites: A combined high resolution 29Si MAS NMR and DFT/MM study on zeolite Beta polymorph C (BEC)

We employed density functional theory/molecular mechanics (DFT/MM) calculations and 29Si magic-angle spinning (MAS) NMR spectroscopy to investigate the effect of single and multiple Ge/Si substitutions on the 29Si NMR parameters as well as the local geometry of SiO4 tetrahedra of the nearest (Ge-O-Si) and next-nearest (Ge-O-Si-O-Si) neighboring Si atoms. The influences of the Ge/Si substitutions are compared with the effects of the corresponding Al/Si substitutions (i.e., Al-O-Si and Al-O-Si-O-Si, respectively). Zeolite Beta polymorph C (BEC), containing double four-membered rings (D4Rs) and exhibiting three distinguishable T sites in the framework, was chosen for this study as a model of germanium containing zeolites. Our computations give a systematic downshift of the 29Si chemical shift of Si by 1–6 ppm for Ge-O-Si sequences. Furthermore, the contributions of two, three, and four Ge atoms as the nearest neighbors to the downshift of Si are not additive and the calculated downshifts lie in the intervals from 2 to 6 ppm, from 1 to 9 ppm, and from 5 to 11 ppm, respectively. Conversely, the contributions of two, three, and four Al atoms as the nearest neighbors are approximately additive. The downshifts caused by Ge nearest neighbors are less than half compared with the corresponding downshifts caused by Al. Moreover, our calculations show that there are no systematic contributions of Ge and Al as next-nearest neighbors (i.e., Ge-O-Si-O-Si and Al-O-Si-O-Si, respectively) to the 29Si chemical shift of Si, and not even the direction (sign) can be predicted without calculating the corresponding sequence.