77Se and 87Rb Solid state NMR study of the structure of Rb2[Pd(Se4)2].Se8.

The structure of Rb(2)[Pd(Se(4))(2)].Se(8) has been investigated using (87)Rb magic angle spinning and static NMR and (77)Se magic angle spinning NMR. The number and the integrated intensities of the (87)Rb and (77)Se resonances are in full agreement with the crystallographic structure of the compound. The (87)Rb and (77)Se nuclear spin interaction parameters have been used to characterize the main structural units of the compound: infinite [Rb(Se(8))](x)(x+) columns and polymeric [Pd(Se(4))(2)](x)(2x-) sheet anions.

Pure absorption-mode spectra using a modulated RF mixing period in MQMAS experiments.

Different approaches to obtain pure absorption-mode lineshapes in MQMAS experiments employing a train of 180 degrees phase-alternating pulses for the multiple-quantum to single-quantum mixing period are investigated. Four pulse sequences, which achieve this by using either the shifted-echo approach or the hypercomplex approach with symmetric coherence transfer pathways, are presented and their improved lineshape- and sensitivity-performance is experimentally demonstrated by (87)Rb MQMAS of RbNO(3). Compared to the original modulated-rf mixing sequence, sensitivity enhancements by factors up to 1.3 are obtained with the sequences described here.

Small crystals and small coils in variable-temperature single-crystal NMR.

Time savings by a factor of between 20 and 30 in the acquisition of multinuclear single-crystal (SC) NMR spectra have been obtained for submillimeter-size (0.01 to 0.03 mm(3)) single crystals when compared to recent results for (31)P and (87)Rb SC NMR. This gain in sensitivity is achieved by optimizing the filling factor using the smallest possible rf coil (2.0 mm inner diameter) for the specific SC probe design. Furthermore, this small coil is particularly useful for variable-temperature SC NMR studies. A probe design for such studies is presented and demonstrated experimentally.

New rubidium zinc hydrogen phosphate, Rb2Zn2(HPO4)3: synthesis, crystal structure, and 31P single-crystal NMR.

A new rubidium zinc hydrogen phosphate, Rb2Zn2(HPO4)3, is prepared by an unusual method utilizing long nucleation times. This material is crystallized from a gel with an initial composition of 1.0 ZnO/0.94 P2O5/0.96 Rb2O/0.04 Li2O/41 H2O, while the phosphate concentration equals 1.6 M and pH = 3.5. The gel is placed in a sealed Pyrex flask at 52 degrees C, and after 4.5 months crystallization of Rb2Zn2(HPO4)3 is noticed. This new crystalline compound has a three-dimensional framework structure built from spiral chains of alternating PO4 and ZnO4 tetrahedra connected pairwise and assembled by other PO4 tetrahedra, rubidium ions, and hydrogen bonds. The two rubidium ions, Rb(1) and Rb(2), have an exceptionally low number of oxygen contacts in the first coordination sphere, five and seven, respectively. Crystal data: monoclinic, P2(1)/c (no. 14), a = 12.5880(4), b = 12.7170(8), c = 7.5827(8) A, beta = 96.100(1) degrees, Z = 4. A single-crystal 31P NMR investigation of Rb2Zn2(HPO4)3 was performed employing a two-axis goniometer probe and reveals the presence of three chemically and six magnetically nonequivalent phosphorus sites, in accordance with the crystal structure. 31P chemical shielding anisotropies and isotropic chemical shifts (-3.3(3), -2.6(3), and 2.0(3) ppm) have been determined for the three phosphorus sites.

Solid-state 87Rb NMR of RbVO3. A comparison of experiments for retrieving chemical shielding and quadrupole coupling tensorial interactions.

Solid-state 87Rb NMR spectra for a powder and single crystal of RbVO3 have been acquired for the central transition at two magnetic field strengths (9.4 and 14.1 T) and using two single-crystal NMR probes of different design. The powder spectra have been obtained using spin-echo techniques without sample spinning because the widths of the spectra are in the range 100-150 kHz. The spectra are analyzed in terms of the chemical shielding and quadrupole coupling interactions and the parameters are compared in an evaluation of the precision for the techniques. Parameters of high precision including the relative orientation for the two tensors are obtained from the single-crystal spectra at 14.1 T. Finally, the orientations of the two tensors in the crystal frame are deduced from the crystal symmetry and an XRD analysis.

71Ga NMR of reference GaIV, GaV, and GaVI compounds by MAS and QPASS, extension of gallium/aluminum NMR parameter correlation.

We report new measurements of NMR parameters for 71Ga in gallium bearing oxide reference compounds, ranging from perfectly ordered systems to disordered crystalline structures and their aluminate counterparts. Static, MAS, and QPASS spectra are obtained at magnetic fields ranging from 7.0 to 18.8 T. With these results we enhance the previously established correlation between isotropic chemical shifts of 71Ga and 27Al and propose a correlation between gallium and aluminum electric field gradients (EFG). This correlation shows that the EFG at 71Ga sites are generally three times greater than those at equivalent 27Al sites.

Improved hardware and software for single-crystal NMR spectroscopy.

Design of state-of-the-art instrumentation and software for acquisition and analysis of single-crystal NMR spectra is presented. The design involves highly accurate rotation of a goniometer, and the acquisition of all the spectra for each rotation axis is automatically controlled by the host computer of the spectrometer using a homebuilt interface between the computer and the single-crystal probe. Moreover, a software package (ASICS) for fast and routine assignment/analysis of complex single-crystal spectra has been developed. Employing this equipment, the acquisition and complete analysis of single-crystal NMR spectra may be performed in about the same time as required for powder methods (spinning or static). The hardware and software are compared to recent alternative approaches within single-crystal NMR. Finally, it has been observed that single-crystal NMR techniques may provide the desired data for samples where powder methods fail.