John E. C. Wren

Structural insights into bound water in crystalline amino acids: experimental and theoretical 17O NMR

We demonstrate here that the (17)O NMR properties of bound water in a series of amino acids and dipeptides can be determined with a combination of nonspinning and magic-angle spinning experiments using a range of magnetic field strengths from 9.4 to 21.1 T. Furthermore, we propose a (17)O chemical shift fingerprint region for bound water molecules in biological solids that is well outside the previously determined ranges for carbonyl, carboxylic, and hydroxyl oxygens, thereby offering the ability to resolve multiple (17)O environments using rapid one-dimensional NMR techniques. Finally, we compare our experimental data against quantum chemical calculations using GIPAW and hybrid-DFT, finding intriguing discrepancies between the electric field gradients calculated from structures determined by X-ray and neutron diffraction.

Solid State Complex Chemistry: Formation, Structure, and Properties of Homoleptic Tetracyanamidogermanates RbRE[Ge(CN2)4] (RE = La, Pr, Nd, Gd)

Tetracyanamidometallates with the general formula RbRE[T(CN2)4] (RE = La, Pr, Nd, Gd; T = Si, Ge) were prepared by solid state metathesis reactions starting from stoichiometric mixtures of RECl3, A2[TF6], and Li2(CN2). Reactions were studied by differential thermal analysis that showed ignition temperatures between 360 and 390 °C for the formation of RbGd[T(CN2)4] with T = Si and Ge. The powder diffraction patterns of RbRE[Ge(CN2)4] were indexed isotypically to the already known RbRE[Si(CN2)4] compound. IR spectra of RbLa[Ge(CN2)4] were measured and compared with those of RbLa[Si(CN2)4]. (73)Ge, (87)Rb, and (139)La solid state NMR measurements and density functional theory calculations were used to verify the novel homoleptic [Ge(CN2)4](4-) ion. Luminescence properties of Eu(3+), Ce(3+), and Tb(3+) doped samples are reported.

Properties and structural investigation of gallophosphate glasses by 71Ga and 31P nuclear magnetic resonance and vibrational spectroscopies

The structure and optical properties of new gallophosphate glasses in the pseudo-binary system xGa2O3 − (100 − x) NaPO3 (x = 0 to 30 mol%), have been investigated. The effect of the progressive addition of Ga2O3 on the local glass structure has been evaluated using Raman and infrared spectroscopies, and 71Ga and 31P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. 71Ga MAS NMR spectra collected at ultrahigh magnetic field (21.1 T) and fast spinning rates (60 kHz) permit the quantification of gallium in 4-, 5- and 6-fold coordination as a function of the Ga2O3 concentration. At low concentrations of Ga2O3, high-coordinate gallium coordinates to oxygens associated with the phosphate chains, increasing the dimensionality and strengthening the glassy network. At moderate Ga loadings, tetrahedral Ga is incorporated into the phosphate chains, introducing additional branching sites which further enhances network connectivity. Higher Ga2O3 content results in the formation of Ga–O–Ga bonds, thereby inhibiting glass formation. 31P MAS NMR and Raman and infrared spectroscopies provide complementary information about the distribution and connectivity of the phosphate groups within the glass network, supporting a structural model which is correlated with the measured optical and thermal properties of the Ga2O3–NaPO3 glasses as a function of the Ga2O3 concentration.

Crystal structure refinements of borate dimorphs inderite and kurnakovite using 11 B and 25 Mg nuclear magnetic resonance and DFT calculations

Abstract Borate minerals composed of [Bφ3] triangles and/or [Bφ4] tetrahedra (φ = O or OH) commonly exhibit complex polymerizations to form diverse polyanion groups. High-resolution solid-state magic angle spinning (MAS) 11B and 25Mg NMR spectroscopy at moderate to ultrahigh magnetic fields (9.4, 14.1, and 21.1 T) allows for very accurate NMR parameters to be obtained for the borate dimorphs, inderite, and kurnakovite, [MgB3O3(OH)5·5H2O]. Improved agreement between experimental results and ab initio density functional theory (DFT) calculations using Full Potential Linear Augmented Plane Wave (FP LAPW) with WIEN2k validates the geometry optimization procedures for these minerals and permits refinements of the hydrogen positions relative to previous X-ray diffraction crystal structures. In particular, the optimized structures lead to significant improvements in the positions of the H atoms, suggesting that H atoms have significant effects on the 11B and 25Mg NMR parameters in inderite and kurnakovite. This study shows that combined high-resolution NMR spectroscopy and ab initio theoretical modeling provides an alternative method for the refinement of crystal structures, especially H positions.

Multinuclear Magnetic Resonance Investigation of Crystalline Alkali Molybdates

A variety of crystalline alkali molybdate phases are characterized by (23)Na, (133)Cs, and (95)Mo magic-angle-spinning nuclear magnetic resonance (MAS NMR) to provide spectroscopic handles for studies of devitrification products in borosilicate nuclear waste glasses. The NMR parameters obtained from line-shape simulations are plotted as a function of various structural parameters to discern trends that may prove useful in the determination of unknown phases. These are applied to Cs3Na(MoO4)2, the most common precipitate found in cesium- and molybdenum-bearing model nuclear waste glasses, the crystal structure of which has not yet been determined, to provide structural constraints that may guide the refinement of powder X-ray diffraction data.

11 B and 23Na solid-state NMR and density functional theory studies of electric field gradients at boron sites in ulexite

Nuclear magnetic resonance (NMR) parameters of 11B in borates and borosilicates, unlike those of many other nuclei such as 29Si and 27Al, vary only over limited ranges and have been thought to be insensitive to local structural environments. High-resolution NMR spectroscopy at high (14 T) and ultrahigh (21 T) fields yield precise 11B and 23Na NMR parameters for ulexite, which contains the pentaborate polyanion ([B5O6(OH)6]3−) as the fundamental building block (FBB). These NMR parameters are compared with ab initio theoretical calculations as implemented in WIEN2K, including optimization of the ulexite structure, determination of the electric field gradients (EFG) and consequently the nuclear quadrupole interaction (QI) parameters at the five distinct B sites, and calculations of the density of states (DOS). These calculations show that the magnitudes and signs of the EFG for [3]B and [4]B are determined by multiple factors, including the electron distributions in the B 2pz orbitals and their interactions with Ca-3p/O-2s orbitals. Most importantly, the calculated B 2pz orbitals at all B sites in ulexite are predominantly affected by the atoms within the fundamental building block, resulting in the insensitivity of the 11B QI parameters to the weak interunit interactions among FBB. Calculations with the water molecules removed from the ulexite structure provide further support for the strong intraunit interactions in FBB as a cause for the poor sensitivity of 11B NMR parameters to local structural environments, including hydrogen bonding, in borates.