Probing Local Environments in Paramagnetic Europium-Substituted Keggin Solids by 31P Magic Angle Spinning NMR Spectroscopy
W. Huang et al.
Paramagnetic Eu-substituted Keggin oxopolytungstates crystallize in different forms, determined by the nature of the counterions. The crystal packing is in turn responsible for the variations in the geometry of paramagnetic Eu sites with respect to the anion core. We probed the paramagnetic environments in a series of Eu-substituted Keggin solids, by 31P magic angle spinning NMR spectroscopy. 31P spinning sideband envelopes are dominated by the electron-nuclear dipolar interaction. For the compounds under investigation, both the magnitude and the asymmetry parameter of the electron-nuclear dipolar coupling tensor are sensitive to the mutual arrangements of paramagnetic Eu sites in the crystal lattice. and also report on the stoichiometry of the anion. The electron-nuclear dipolar coupling tensors were calculated from the crystallographic coordinates and the experimentally determined effective magnetic moments, assuming a point dipole approximation. The computed tensors are in very good agreement with the experimental spectra. Furthermore, the P-Eu distance estimates, accurate to within 0.06-0.12 A, can be obtained directly from the magnitude of the electron-nuclear dipolar coupling. This work demonstrates that 31P MAS NMR spectroscopy is a useful probe for investigating local environments in paramagnetic Keggin solids.
Oxygen Sites and Network Coordination in Sodium Germanate Glasses and Crystals: High Resolution Oxygen-17 and Sodium-23 NMR.
L.S. Du and J.F. Stebbins
Sodium germanate glasses are well-studied materials in which, unlike silicates but analogous to borates, the major structural consequence of alkali addition is generally thought to involve a coordination number increase of the network-forming Ge cations. However, the nature of this change, in particular quantifying fractions of nonbridging oxygens and of five- and/or six-coordinated Ge, has remained unresolved. We present here highresolution 17O results, including triple-quantum MAS NMR (3QMAS), on a series of crystalline model compounds that allow the definition of ranges of chemical shifts corresponding to oxygens bonded to various coordinations of Ge. These include quartz- and rutile-structured GeO2, Na4Ge9O20, Na2Ge4O9, and Na2GeO3 (germanium dioxide, sodium enneagermanate, sodium tetragermanate, and sodium metagermanate). 3QMAS spectra of Na-germanate glasses ranging from 0% to 27% Na2O clearly show the development of partially resolved peaks as alkali is added, corresponding to signals from nonbridging oxygens (in the highest Na glasses) and to oxygen bridging between one four-coordinated and one higher coordinated Ge. As in conventional models of this system, nonbridging oxygen contents are much lower than in corresponding silicates. Although we do not directly distinguish between five- and six-coordinated Ge, modeling of bridging oxygen populations and comparison with measured speciation suggest that substantial proportions of both species are likely to be present. High-field 23Na MAS NMR shows systematic decreases in mean Na-O bond distance and/or coordination number with increasing alkali content that can be compared with published results for high-temperature liquids. These results, as well as comparison of molar volumes of glasses and high-temperature liquids, suggest the possibility of significant temperature effects on liquid structure.
Photochemical Fine-Tuning of Luminescent Coloout on Cadmium Selenide Nanoparticles: Fabricating a Single-Source Multicolor Luminophore.
T. Torimoto et al.
Size-selective photoetching was applied to silica-coated cadmium selenide (SiO2/CdSe) nanoparticles to precisely control their photoluminescence properties. The absorption spectra of CdSe was blue-shifted by irradiation of monochromatic light, and finally, the absorption onset agreed with the wavelength of irradiation light, indicating that CdSe particles were photoetched to smaller ones until the irradiated photons were not absorbed by the photoetched particles and that the SiO2 shell layer surrounding the CdSe core prevented coalescence between the photoetched particles. Although as-prepared SiO2/CdSe did not exhibit photoluminescence, the application of size-selective photoetching to SiO2/CdSe resulted in the development of the band gap emission, with the degree being enhanced with progress of the photoetching. The peak wavelength of photoluminescence decreased with a decrease in the wavelength used for the photoetching, so that the luminescence color could be tuned between red and blue. Partial photoetching of SiO2/CdSe nanoparticle films produced intense band gap emission of CdSe at the photoetched area, while the remainder of the SiO2/ CdSe films did not exhibit detectable photoluminescence, resulting in the formation of a clear photoluminescence image under UV irradiation. This technique makes it possible to produce a multicolored photoluminescence image by irradiation with monochromatic lights having various wavelengths using a single source material.
Synthesis, crystal structure and magnetic properties of an alternating manganese chain.
M.R. Silva et al.
JSolidStateChem (2006) 179, 2054.
A new 1D complex has been prepared and characterized. X-ray single crystal structure con.rms that the Mn(II) ions assemble in alternating chains with Mn–Mn distances of 3.8432(13) and 4.4428(14)A . A 3D network of hydrogen bonds links the chains together. The temperature dependence of the magnetic susceptibility reveals that this compound undergoes a magnetic transition and exhibits an antiferromagnetic interaction in the low-temperature phase with two alternating exchange interactions of -2.32(1) and -5.55(1)cm-1.
Sr4PbPt4O11, the first platinum oxide containing Pt2 6+ ions.
C. Renard et al.
JSolidStateChem (2006) 179, 2054.
We report the synthesis and crystal structure of the new compound Sr4PbPt4O11, containing platinum in highly unusual square pyramidal coordination. The crystals were obtained in molten lead oxide. The structure was solved by X-ray single crystal diffraction techniques on a twinned sample, the final R factors are R = 0.0260 and wR = 0.0262. The symmetry is triclinic, space group P1¯ , with a = 5.6705(6) A, b = 9.9852(5) A, c = 10.0889(5) A, alpha = 90.421(3), beta = 89.773(8), gamma = 90.140(9) and Z = 2. The structure is built from dumbell-shaped Pt2O9 entities formed by a dinuclear metal–metal bonded Pt2 6+ ion with asymmetric environments of the two Pt atoms, classical PtO4 square plane and unusual PtO5 square pyramid. Successive Pt2O9 entities deduced from 901 rotations are connected through the oxygens of the PtO4 basal squares to form (Pt4O10)-8 columns further connected through Pb2+ and Sr2+ ions. Raman spectroscopy confirmed the peculiar platinum coordination environment.
Structural and 31P NMR investigation of Bi(MM')2PO6 statistic solid solutions: Deconvolution of lattice constrants and cationic influences.
M. Colmont et al.
JSolidStateChem (2006) 179, 2111.
Two solid solutions BiMxMg(2-x)PO6 (with M2+ = Zn or Cd) have been studied through 31P MAS NMR. The analysis has been performed on the basis of re.ned crystal structures through X-ray diffraction and neutron diffraction. The BiZnxMg(2-x)PO6 does not provide direct evidence for sensitive changes in the phosphorus local symmetry. This result is in good agreement with structural data which show nearly unchanged lattices and atomic separations through the Zn2+ for Mg2+ substitution. On the other hand, the Cd2+ for Mg2+ substitution behaves differently. Indeed, up to five resonances are observed, each corresponding to one of the five first-cationic neighbour distributions, i.e. 4Mg/0Cd, 3Mg/1Cd, 2Mg/2Cd, 1Mg/3Cd and 0Mg/4Cd. Their intensities match rather well the expected weight for each con.guration of the statistical Cd2+/Mg2+ mixed occupancy. The match is further improved when one takes into account the in.uence of the 2nd cationic sphere that is available from high-.eld NMR data (18.8 T). Finally, the fine examination of the chemical shift for each resonance versus x allows to de-convolute the mean Z/a2 effective field into two sub-effects: a lattice constraint only term and a chemical-only term whose effects are directly quantifiable.