Molybdenum Oxide Nitrides of the Mo2(O,N,□)5 Type: On the Way to Mo2O5.

Blue-colored molybdenum oxide nitrides of the Mo2(O,N,□)5 type were synthesized by direct nitridation of commercially available molybdenum trioxide with a mixture of gaseous ammonia and oxygen. Chemical composition, crystal structure, and stability of the obtained and hitherto unknown compounds are studied extensively. The average oxidation state of +5 for molybdenum is proven by Mo K near-edge X-ray absorption spectroscopy; the magnetic behavior is in agreement with compounds exhibiting MoVO6 units. The new materials are stable up to ∼773 K in an inert gas atmosphere. At higher temperatures, decomposition is observed. X-ray and neutron powder diffraction, electron diffraction, and high-resolution transmission electron microscopy reveal the structure to be related to VNb9O24.9-type phases, however, with severe disorder hampering full structure determination. Still, the results demonstrate the possibility of a future synthesis of the potential binary oxide Mo2O5. On the basis of these findings, a tentative suggestion on the crystal structure of the potential compound Mo2O5, backed by electronic-structure and phonon calculations from first principles, is given.

Tuneable anisotropy and magnetism in Sn2Co3S2-xSex - probed by (119)Sn Mößbauer spectroscopy and DFT studies.

The half metal (HFM) Sn2Co3S2 shows a fascinating S = 1/2 magnetism. Anisotropic coupling of spins in and between Co Kagomé layers by Sn sites is now studied from the substitution effects of S by Se by systematic and local experimental and first principles data. Trends in crystal structure changes (c/a ratio) as retrieved from XRD data on the solid solution Sn2Co3S2-xSex are complemented by DFT modelling on Sn2Co3SeS and hitherto unknown Sn2Co3Se2. The relationship of crystal structure effects with changes in Curie temperatures and magnetic hysteresis is shown from susceptibility measurements. An insight into the role of the Sn sites in magnetism and bonding is gained from (119)Sn Mössbauer spectroscopic measurements. Isomer shifts, quadrupole splitting, and magnetic hyperfine fields are interpreted by DFT calculations on chemical bonding, electric field gradients (EFG), Fermi contact, and spin polarization.

Synthesis and characterization of inorganic-organic hybrid materials based on the intercalation of stable organic radicals into a fluoromica clay.

Hybrid materials, in which stable organic radical cations are intercalated into layered inorganic host materials, can be successfully synthesized via an ion exchange reaction in a layered fluoromica clay, to yield recyclable heterogeneous catalysts for oxidation of various alcohols. We have conducted systematic synthetic and structural studies on the intercalation of the radical cations 4-(diethylmethylammonium)-2,2,6,6-tetramethylpiperidin-1-oxyl (DEMTEP), 1-[2-(4-amino-2,2,6,6-tetramethyl-1-piperidinyloxyl)-2-oxoethyl]-1'-methyl-4,4'-bipyridinium (VIOTEP), and 2-(3-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide (m-MPYNN) into a synthetic fluoromica clay named Somasif® ME 100, Na(2x)Mg(3.0-x)Si4O10(F(y)OH(1-y))2 (x = 0.33, y = 0.98). The guest-host interactions in these intercalation compounds have been characterized by X-ray powder diffraction and solid-state NMR of the constituent nuclei ((23)Na, (19)F, and (29)Si) of the Somasif structure. The intercalation process can be conveniently monitored using (23)Na MAS-NMR. Guest-guest interactions have been probed by magnetic susceptibility measurements as well as EPR and (1)H MAS NMR experiments. The (1)H MAS-NMR line widths and chemical shifts probe modifications in the electron spin density distributions and/or intermolecular interactions between the electron spins of the guest species. Despite these indications of weakly interacting spins, magnetic susceptibility measurements are consistent with the near-absence of cooperative magnetism. The VIOTEP and DEMTEP inclusion compounds demonstrate catalytic activity for the oxidation of benzyl alcohol, using NaOCl as a co-oxidant. Although the radical ion species is partially leached out under these conditions (ionic exchange with Na(+) in solution) the catalytic activity remains for up to 40 subsequent cycles. Fully leached materials can be regenerated by catalyst re-loading and this process can be conveniently monitored by X-band EPR spectroscopy.

Noninteracting, vicinal frustrated P/B-Lewis pair at the norbornane framework: synthesis, characterization, and reactions.

Hydroboration of dimesitylnorbornenylphosphane with Piers' borane [HB(C6F5)2] gave the frustrated Lewis pair (FLP) 4 in good yield. It has the -PMes2 Lewis base attached at the 2-endo position and the -B(C6F5)2 group 3-exo oriented at the norbornane framework. The vicinal FLP 4 was shown by X-ray diffraction and by spectroscopy to be a rare example of an intramolecular noninteracting pair of a Lewis acid and Lewis base functionality. The FLP 4 rapidly splits dihydrogen heterolytically at ambient temperature to yield the phosphonium/hydrido borate zwitterion 5. It adds to the carbonyl group of benzaldehyde and to carbon dioxide to yield the adducts 6 and 7, respectively. Compounds 5-7 were characterized by X-ray diffraction. Compound 4 adds to the S═O function of sulfur dioxide to give a pair of diastereomeric heterocyclic six-membered ring products due to the newly formed sulfur chirality center, annulated with the norbornane skeleton, which were investigated by (31)P/(11)B single and double resonance solid state NMR experiments. Compound 8 was also characterized by X-ray diffraction. The FLP 4 undergoes a clean N,N-addition to nitric oxide (NO) to give a norbornane annulated five-membered heterocyclic persistent FLP-NO aminoxyl radical 12 (characterized, e.g., by X-ray diffraction and EPR spectroscopy). Additionally, the FLP radical was characterized by (1)H solid state NMR spectroscopy. The radical 12 undergoes a H-atom abstraction reaction with 1,4-cyclohexadiene to yield the respective diamagnetic FLP-NOH product 13, which was also characterized by X-ray diffraction and solid state NMR spectroscopy.