Modified polyoxometalates: Hydrothermal syntheses and crystal structures of three novel reduced and capped Keggin derivatives decorated by transition metal complexes

Three novel polyoxometalate derivatives decorated by transition metal complexes have been hydrothermally synthesized. Compound 1 consists of [(PMo6Mo2V8O44)-Mo-VI-V-V-O-IV{CO (2,2'-bipy)(2)(H2O)}(4)](3+) polyoxocations and [(PMo4Mo4V8O44)-Mo-IV-V-V-O-IV{Co(2,2'-bipy)(2)(H2O)}(2)](3-) polyoxoanions, which are both built on mixed-metal tetracapped [PMo8V8O44] subunits covalently bonded to four or two {Co(2,2'-bpy)(2)(H2O)}(2+), clusters via terminal oxo groups of the capping V atoms. Compound 2 is built on [(PMo8V6O42)-V-VI-O-IV{Cu-I(phen)}(2)](5-) clusters constructed from mixed-metal bicapped [(PMo8V6O42)-V-VI-O-IV](7-) subunits covalently bonded to two {Cu(phen)}(+) fragments in the similar way to 1. The structure of 3 is composed of [(PMo9Mo3O40)-Mo-VI-O-V](6-) units capped by two divalent Ni atoms via four bridging oxo groups.

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)(2)}(2)V4O12]center dot 5H(2)O and [Ni(phen)(3)](2)[V4O12]center dot 17.5H(2)O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen(2))(2)V4O12].5H(2)O (1) and [Ni(phen)(3)](2)[V4O12] . 17.5H(2)O (2). Crystal data: C48H52Cd2N8O22V4 (1), triclinic. P (1) over bar, a = 10.3366(10), b = 11.320(3), c = 13.268(3) Angstrom, alpha = 103.888(17)degrees, beta = 92.256(15)degrees, gamma = 107.444(14)degrees, Z = 1; C72H131N12Ni2O29.5V4 (2), triclinic. P (1) over bar, a = 12.305(3), b = 13.172(6), c = 15.133(4), alpha = 79.05(3)degrees, beta = 76.09(2)degrees, gamma = 74.66(3)degrees, Z = 1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59degrees < theta < 26.02degrees and 2.01degrees < 0 < 25.01degrees using the omega-scan technique, respectively. The structure of 1 consists of a [V4O12](4-) cluster covalently attached to two {Cd(phen)(2)}(2+) fragments, in which the [V4O12](4-) cluster adopts a chair-like configuration. In the structure of 2, the [V4O12](4-) cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the V4O12](4-) unit and crystallization water molecules.

Hydrothermal syntheses and crystal structures of new cage-like mixed-valent polyoxovanadates

Three new cage-like mixed-valent polyoxovanadates [Ni(1,10'-phen)(3)](2)[V10O26] 1, [Zn(2,2'-biPY)(3)](3)[V15O36Cl](.)3H(2)O (2) and [Co(2,2'-biPY)(3)](3)[V15O36Cl](.)3H(2)O (3) have been hydrothermally synthesized for the first time and characterized by elemental analyses, IR, EPR spectra, TG analyses and single crystal X-ray diffraction. The polyoxoanion of I exhibits an interesting empty ellipsoidal [V-2(IV) V-8(V) O-26](4-) 'host' shell, while the oxo vanadium clusters of 2 and 3 possess a spherical [V-8(IV) V-7(V) O36Cl](6-) cage with a Cl- ion encapsulated. The structure-directing role of organic templates (1,10'-phen and 2,2'-bipy) on the formation of the polyoxoanion structures is discussed.

The first polyoxometalate polymer constructed by assembly of the heptamolybdic anion and copper coordination groups

The first example of one-dimensional organic-inorganic polymetallic coordination polymer based on heptamolybdate anions, formulated (NH4)[Cu(en)(2)][Na(en)Cu(en)(2)(H2O)(Mo7O24)].4H(2)O (en = ethylenediamine) (1) has been hydrothermally synthesized and characterized by element analysis, IR, EPR, CV and single crystal X-ray diffraction. The structure of 1 is fabricated by self-assembly of integrated heptamolybdic anions without collapse of primary structure and copper-ethylenediamine(en) coordination groups into one-dimensional zigzag-shaped chains.

Metal-organic frameworks based on the pyridine-2,3-dicarboxylate and a flexible bispyridyl ligand: syntheses, structures, and photoluminescence

Three new metal-organic coordination polymers, [Cu(2,3-pydc)(bpp)]center dot 2.5H(2)O (1), [Zn(2,3-pydc)(bpp)]center dot 2.5H(2)O (2) and [Cd(2,3-pydc)(bpp)(H2O)]center dot 3H(2)O (3) (2,3-pydcH(2) = pyridine-2,3-dicarboxylic acid, bpp 1,3-bis(4-pyridyl)propane), have been synthesized at room temvperature. All complexes have metal ions serving as 4-connected nodes but represent two quite different structural motifs. Complexes 1 and 2 are isomorphous, both of which feature 2D -> 3D parallel interpenetration. Each two-dimensional (2D) layer with (4, 4) topology is interlocked by two nearest neighbours, one above and one below, thus leading to an unusual 3D motif. Complex 3 has a non-interpenetrating 3D CdSO4 framework with cavities occupied by uncoordinated water molecules.

Syntheses, crystal structures and properties of two Cu(II) coordination polymers: Cu(C3N2H4)(2)(HL)(2) andCU(C3N2H4)(2)L with C3N2H4 = imidazole, H2L = adipic acid

The reactions of freshly prepared Cu(OH)(2).xH(2)O and Cu(OH)(2-2y)(CO3)(y).zH(2)O precipitates with imidazole and adipic acid in CH3OH/H2O at pH = 5.4 yielded CU(C3N2H4)(2)(HL)(2) 1 and CU(C3N2H4)(2)L 2, respectively. Complex 1 consists of ribbon-like polymeric chains (1)(infinity)[CU(C3N2H4)(2)(HL)(4/2)], in which the octahedrally coordinated Cu atoms are doubly bridged by bis-monodentate hydrogen adipato ligands. The interchain N-H...O hydrogen bonding interactions are responsible for supramolecular assembly of the polymeric chains into open 3D frameworks and two-fold interpenetration of the resulting open frameworks completes the crystal structure of 1. Within complex 2, the Cu atoms are penta-coordinated to form CuN2O3 square pyramids and condensed into CU2N4O4 dimers, which are doubly bridged by twisted bis-monodentate adipato ligands into polymeric chains (1)(infinity)([CU(C3N2H4)(2)](2)L-4/2) with 4- and 18-membered rings progressing alternatively. The polymeric chains are assembled due to interchain N-H...O hydrogen bonding interactions. The thermal and magnetic behaviors of 1 and 2 is discussed.

Hydrothermal Wave in a Shallow Liquid Layer

The oscillatory thermocapillary convection and hydrothermal wave in a shallow liquid layer, where a temperature difference is applied between two parallel sidewalls, have been numerically investigated in a two-dimensional model. The oscillatory thermocapillary convection and hydrothermal wave appear if the Marangoni number is larger than a critical value. The critical phase speed and critical wave number of the hydrothermal wave agree with the ones given analytically by Smith and Davis in the microgravity environment, and it travels in the direction opposed to the surface flow. Another wave traveled downstream in addition to the hydrothermal wave traveled upstream was observed in the case of earth gravity condition.

The Hydrothermal Wave Of Large-Prandtl-Number Fluid In A Shallow Cavity

The hydrothermal wave was investigated numerically for large-Prandtl-number fluid (Pr = 105.6) in a shallow cavity with different heated sidewalls. The traveling wave appears and propagates in the direction opposite to the surface flow (upstream) in the case of zero gravity when the applied temperature difference grows and over the critical value. The phase relationships of the disturbed velocity, temperature and pressure demonstrate that the traveling wave is driven by the disturbed temperature, which is named hydrothermal wave. The hydrothermal wave is so weak that the oscillatory flow field and temperature distribution can hardly be observed in the liquid layer. The exciting mechanism of hydrothermal wave is analyzed and discussed in the present paper.

Hydrothermal Instability Of Thermocapillary Convection In Large-Prandtl-Number Liquid Bridges Under Microgravity

Linear stability analysis was performed to study the mechanism of transition of thermocapillary convection in liquid bridges with liquid volume ratios ranging from 0.4 to 1.2, aspect ratio of 0.75 and Prandtl number of 100. 2-D governing equations were solved to obtain the steady axi-symmetric basic flow and temperature distributions. 3-D perturbation equations were discretized at the collocation grid points using the Chebyshev-collocation method. Eigenvalues and eigenfunctions were obtained by using the Q-R. method. The predicted critical Marangoni numbers and critical frequencies were compared with data from space experiments. The disturbance of the temperature distribution on the free surface causes the onset of oscillatory convection. It is shown that the origin of instability is related to the hydrothermal origin for convections in large-Prandtl-number liquid bridges. (C) 2007 COSPAR. Published by Elsevier Ltd. All rights reserved.

Growth of composite sapphire/Ti : sapphire by the hydrothermal method

Composite sapphire/Ti:sapphire crystals for high-power laser application were grown by the hydrothermal method. The results of the X-ray rocking curve analysis indicate high crystalline quality of the surface Al2O3 material. The strong bonding between the overgrown Al2O3 and seed Ti:Al2O3 crystals is indispensable for withstanding high thermal stresses produced by intense optical pumping. The optical loss at the boundary of the composite crystal is considerably low, indicating the lack of scattering centers. (c) 2005 Elsevier B.V. All rights reserved.

Low-temperature hydrothermal growth of oriented [0001] ZnO film

Well-aligned ZnO films have been successfully prepared by using low-temperature hydrothermal approach on (0001) sapphire substrates that were pre-coated with a ZnO nano-layer by dip-coating. The characterizations of scanning electron microscopy (SEM) and X-ray diffraction (XRD) indicate that the ZnO films consist of hexagonal rods that grow along the c axis based on the sapphire substrates. It is found that the size of ZnO rods can be adjusted by an aqueous solution with some methenamine. (c) 2006 Elsevier B.V. All rights reserved.

Hydrothermal growth and characterization of ZnO crystals

ZnO crystals with dimensions of 30 x 38 x 8 turn 3 have been grown by the hydrothermal method using a mixed solution of KOH, LiOH and H2O2. The growing rates for +c(0001) and -c(000 (1) over bar) were 0.17 and 0.09 mm/day, respectively. The crystal color was very light green for +c sector and dark brown for -c sector. For the +c sector, the resistivity at room temperature was 80 0 cm, the carrier concentration was about 10(4)/cm(3), and the mobility was about 100 cm(2)/Vs. The full-width at half-maximum (FWHM) of double axis X-ray rocking curve for the polished Zn face cut from +c sector was 45 arcsec. The photoluminescence (PL) spectrum and the absorption spectrum of +c part of the crystals at room temperature were also reported and discussed in this paper. (c) 2008 Elsevier B.V. All rights reserved.

Syntheses, crystallographic and magnetic properties of Nd3Fe29-xCrx and other associated compounds

A systematic study of syntheses and magnetic properties of the Nd-3 Fe29-xCrx (x=4.5, 4.7, 5.0, and 5.5) compounds has been performed. The single-phase compounds of Nd3Fe29-xCrx can be formed in the range 4.5 less than or equal to x less than or equal to 5.5. The Curie temperature Tc, the saturation magnetization M-S at 4.2 K, the anisotropy field H-A at 4.2 K and room temperature, and the intra-sublattice exchange coupling parameter j(FeFe) at 4.2 K for the Nd3Fe29-xCrx compounds decrease with increasing Cr composition from x=4.5 to 5.5, respectively. Nitrogenation and carbonation, unlike hydrogenation, result mainly in improvements of the Curie temperature, the saturation magnetization and the anisotropy field at 4.2 K and room temperature for the Nd3Fe29-xCrx compounds compared with their parent compounds.

Synthesis of novel hexagon SnO2 nanosheets in ethanol/water solution by hydrothermal process

The novel hexagon SnO2 nanosheets are successfully synthesized in ethanol/water solution by hydrothermal process. The samples are characterized by X-ray diffraction (XRD), infrared ray (IR) and transmission electron microscopy (TEM). By changing the reaction conditions, the size and the morphology can be controlled. Comparison experiments show that when the temperature increased from 140 degrees C to 180 degrees C, the edge length of the hexagon nanoparticles increases from 300-450 nm to 700-900 nm. On the other hand, by adjusting the ratios of water to ethanol from 2 to 0.5, SnO2 nanoparticles with different morphologies of triangle and sphere are obtained. When the concentration of NaOH is increased from 0.15 M to 0.30 M, a hollow ring structure can be obtained. (c) 2006 Elsevier B.V. All rights reserved.