Nanotubes of the disulfides of groups 4 and 5 metals

The layered chalcogenides, having structures analogous to graphite, are known to be unstable toward bending and show high propensity to form curved structures, thus eliminating dangling bonds at the edges. Since the discovery of fullerene and nanotube structures of WS2 and MoS2 by Tenne et al. [1-3], there have been attempts to prepare and characterize nanotubes of other layered dichalcogenides with structures analogous to MoS2. Nanotubes of MoS2 and WS2 were prepared by Tenne et al. by reducing the corresponding oxides to the suboxides followed by heating in an atmosphere of forming gas (5 % H-2 + 95 % N-2) and H2S at 700-900 degreesC [1-3]. Alternative methods of synthesis of MoS2 and WS2 nanotubes have since been proposed by employing the decomposition of the ammonium thiometallates or the corresponding trisulfide precursors. This alternative procedure was based on the observation that the trisulfide seems to be formed as an intermediate in the synthesis of the MoS2 and WS2 nanotubes [4]. Accordingly, the decomposition of the trisulfides of MoS2 and W in a reducing atmosphere directly yielded nanotubes of the disulfides MoS2 and WS2 [5]. In this article, we describe the synthesis, structure, and characterization of a few novel nanotubes of the disulfides of groups 4 and 5 metals. These include nanotubes of NbS2, TaS2, ZrS2, and HfS2. The study enlarges the scope of the inorganic nanotubes significantly and promises other interesting possibilities, including the synthesis of the diselenide nanotubes of these metals.

A comparison of the DNMR behaviour of methyl 5,6-bis(2-methoxyphenyl)-1,4-dimethyl-7-oxobicyclo[2.2.1]hept-5-en-2-endo-carboxylate and its 7-oxa analogue

Methyl 5,6-Bis(2-methoxyphenyt)-1,4-dimethyl-7-oxobicyclo[2.2.1]hept-5-en-2-endo-carboxylate, a moderately crowded norbornenone ester, exhibits complex VT-DNMR behaviour. A similar behaviour is not seen in its 7-oxa analogue, showing that conformational transmission from position 7 has a crucial influence on the distance parameters that govern the dynamic processes involving the substituents on the bicycloheptene framework.

A determination of the structure of the intramolecular charge transfer state of 4-dimethylaminobenzonitrile (DMABN) by time-resolved resonance Raman spectroscopy

Picosecond time-resolved resonance Raman spectra of the A (intramolecular charge transfer, ICT) state of DMABN, DMABN-d(6) and DMABN-N-15 have been obtained. The isotopic shifts identify the nu (s)(ph-N) mode as a band at 1281 cm(-1). The similar to 96 cm(-1) downshift of this mode from its ground state frequency rules out the electronic coupling PICT model and unequivocally supports the electronic decoupling TICT model. However, our results suggest some pyramidal character of the A state amino conformation.

Orthometalation in calixarenes: Synthesis and structural characterization of a novel orthopalladated calix[4]arene bisphosphite

The treatment of a symmetrically bridged p-Bu-t-calix[4] arene bisphosphite with PdCl2(NCPh)(2) yields a novel orthopalladated derivative by a C-C bond scission of a t-butyl group attached to an aryl ring. The structure of this orthopalladated calix[4]arene derivative has been established by X-ray crystallography.

Photochemical behaviour of 4-styrylcoumarin polymorphs in the crystalline state

Addition of a small amount of coumarin during crystallization produces new polymorphic modifications in 4-styrylcoumarin and 4-(3-fluorostyryl)coumarin, which are photolabile. Interestingly, upon irradiation polymorphic modification of 4-(3-fluorostyryl)coumarin produces a mirror-symmetric photodimer in contrast to the centrosymmetric photodimer obtained without addition of coumarin during crystallization.

A layered chlorophosphate, Na-3[Cd4Cl3(HPO4)(2)(H2PO4)(4)], containing Na+ ions in the interlamellar space

Reaction between CdCl2.H2O and NaH2PO4.H2O Under hydrothermal conditions gives rise to a new cadmium chlorophosphate of the formula Na-3[Cd4Cl3(HPO4)(2)(H2PO4)(4)] I. This material crystallizes in the orthorhombic system with space group Fmm2(no. 42). I has macroanionic layers of [Cd4Cl3(HPO4)(2)(H2PO4)(4)](3-) with Na+ ions in the interlamellar space. The discovery of such compounds suggests that metathetic reactions carried out under hydrothermal conditions may provide a novel route for the synthesis of new open-framework structures.

A Layered Zinc Phosphate, [C6N4H22][Zn6(PO4)4(HPO4)2], Formed by One-Dimensional Tubes

An open-framework zinc phosphate, [C6N4H22][Zn6(PO4)4(HPO4)2] (I), with alternating inorganic and organic layers has been synthesized hydrothermally from a starting mixture of ZnO, HCl, H3PO4, H2C2O4, and triethylenetetramine. Single-crystal data for I: monoclinic, space GROUP =P21/c (No. 14), a=9.881(1), b=16.857(1), c=8.286(1) Å, β=96.7(1)°, V=1370.8(1) Å3, Z=2, R1=0.06, and wR2=0.13 [1408 observed reflections with I>2σ(I)]. The structure of I comprises a network of ZnO4, PO4, and PO3(OH) tetrahedra forming one-dimensional tubes. The tubes, in turn, are linked via oxygen atoms forming macroanionic inorganic layers with eight-membered apertures. The one-dimensional tube-like architecture in I is a novel feature worthy of note.

Critical properties of the double-exchange ferromagnet Nd(0.6)Pb(0.4)MnO(3)

Results of a study of dc magnetization M(T,H), performed on a Nd(0.6)Pb(0.4)MnO(3) single crystal in the temperature range around T(C) (Curie temperature) which embraces the supposed critical region \epsilon\=\T-T(C)\/T(C)less than or equal to0.05 are reported. The magnetic data analyzed in the critical region using the Kouvel-Fisher method give the values for the T(C)=156.47+/-0.06 K and the critical exponents beta=0.374+/-0.006 (from the temperature dependence of magnetization) and gamma=1.329+/-0.003 (from the temperature dependence of initial susceptibility). The critical isotherm M(T(C),H) gives delta=4.54+/-0.10. Thus the scaling law gamma+beta=deltabeta is fulfilled. The critical exponents obey the single scaling equation of state M(H,epsilon)=epsilon(beta)f(+/-)(H/epsilon(beta+gamma)), where f(+) for T>T(C) and f(-) for T

(4aR, 8aS, 9aR, 10aS)-8a, 9a-Difluoro-1,4,4a, 5,8,8a, 9,9a, 10,10a-decahydroanthracene-4a, 10a-diol hemihydrate

The title compound, C(14)H(18)F(2)O(2)center dot 0.5H(2)O, a hemihydrate of a C(s)-symmetric unsaturated difluorodiol, crystallizes in the centrosymmetric space group P2/m (Z = 4). The asymmetric unit contains two crystallographically independent difluorodiol half-molecules, occupying the mirror planes at (x, 0, z) and (x, 1/2, z), and half a molecule of water, lying on the twofold axis at (0, y, 0). Four difluorodiol molecules self-assemble around each solvent water molecule via O-H center dot center dot center dot O hydrogen bonds in a near tetrahedral symmetry to generate a cylindrical column-like architecture.

Reduction of oxygen impurity at GaN/beta-Si(3)N(4)/Si interface via SiO(2) to Ga(2)O conversion by exposing of Si surface under Ga flux

The removal of native oxide from Si (1 1 1) surfaces was investigated by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectra (SIMS) depth profiles. Two different oxide removal methods, performed under ultrahigh-vacuum (UHV) conditions, were carried out and compared. The first cleaning method is thermal desorption of oxide at 900 degrees C. The second method is the deposition of metallic gallium followed by redesorption. A significant decrease in oxygen was achieved by thermal desorption at 900 degrees C under UHV conditions. By applying a subsequent Ga deposition/redesorption, a further reduction in oxygen could be achieved. We examine the merits of an alternative oxide desorption method via conversion of the stable SiO(2) surface oxide into a volatile Ca(2)O oxide by a supply of Ga metals. Furthermore, ultra thin films of pure silicon nitride buffer layer were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma followed by GaN growth. The SIMS depth profile shows that the oxygen impurity can be reduced at GaN/beta-Si(3)N(4)/Si interfaces by applying a subsequent Ga deposition/redesorption. (C) 2011 Elsevier B.V. All rights reserved.

Photoluminescence of Sr(2-x)Ln(x)CeO(4+x/2) (Ln = Eu, Sm or Yb) prepared by a wet chemical method

A wet chemical route is developed for the preparation of Sr2CeO4 denoted the carbonate-gel composite technique. This involves the coprecipitation of strontium as fine particles of carbonates within hydrated gels of ceria (CeO2.xH(2)O, 404 with complete phase purity. Doping of other rare-earths is carried out at the co-precipitation stage. The photoluminescence (PL) observed for Sr2CeO4 originates from the Ce4+-O2- charge-transfer (CT) transition resulting from the interaction of Ce4+ ion with the neighboring oxide ions. The effect of next-nearest-neighbor (NNN) environment on the Ce4+-O2- CT emission is studied by doping with Eu3+, Sm3+ or Yb3+ which in turn, have unique charge-transfer associated energy levels in the excited states in oxides. Efficient energy transfer occurs from Ce4+-O2- CT state to trivalent lanthanide ions (Ln(3+)) if the latter has CT excited states, leading to sensitizer-activator relation, through non-resonance process involving exchange interaction. Yb3+-substituted Sr2CeO4 does not show any line emission because the energy of Yb3+-O2- CT level is higher than that of the Ce4+-O2- CT level. Sr2-xEuxCeO4+x/2 shows white emission at xless than or equal to0.02 because of the dominant intensities of D-5(2)-F-7(0-3) transitions in blue-green region whereas the intensities of D-5(0)-F-7(0-3) transitions in orange-red regions dominate at concentrations xgreater than or equal to0.03 and give red emission. The appearance of all the emissions from D-5(2), D-5(1) and D-5(0) excited states to the F-7(0-3) ground multiplets of Eu3+ is explained on the basis of the shift from the hypersensitive electric-dipole to magnetic-dipole related transitions with the variation in site symmetry with increasing concentration of Eu3+. White emission of Sr2-x SmxCeO4+x/2 at xless than or equal to0.02 is due the co-existence of Ce4+-O2- CT emission and (4)G(4)(5/2)-H-6(J) Sm3+ transitions whereas only the Sm3+ red emission prevails for xgreater than or equal to0.03. The above unique changes in PL emission features are explained in terms of the changes in NNN environments of Ce4+. Quenching of Ce4+-O2- CT emission by other Ln(3+) is due to the ground state crossover arising out of the NNN interactions.

Stereochemistry of the marine sesquiterpene 2-thiocyanatoneopupukeanane: Crystal structure of neopupukean-2-yl 4-nitrobenzoate

Single crystal X-ray diffraction analysis of neopupukean-2-yl p-nitrobenzoate unambiguously established the stereochemistry of the thiocyanate group as endo in the marine sesquiterpene 2-thiocyanatoneopupukeanane.

Synthesis based on cyclohexadienes Part 36: an efficient methodology for the construction of spiro[4.5]decanes: a formal synthesis of acorone

An efficient strategy for the contruction of spiro[4.5] decanes is described and involves a bridgehead substitution of a methoxyl group by a methyl group followed by an oxidative cleavage of the tricyclo[5.2.2.0(1,5)] undecane 25 to produce the spiro[4.5] decanes 31 & 32 which are intermediates in the synthesis of acorone. A novel one-pot conversion of alpha-methoxy carboxylic acid to alpha-methyl carboxylic acid is described.