Hydrothermal synthesis and structural characterization of novel alpha-Keggin unit-supported Cu(II)- and Mn(II)-bipyridine complexes from a tri-lacunary precursor

Blue [{Cu(2,2'-bipy)(2)}(2){alpha-SiW12O40}] (bipy = bipyridyl) (1) and pale yellow [Mn(2,2'-bipy)(3)](2)[alpha-SiW12O40] (2) have been synthesized hydrothermally and characterized by IR spectroscopy and single crystal X-ray structure analysis. In 1, the [alpha-SiW12O40](4-) ion acts as a bridge between the two [{Cu(2,2'-bipy)(2)](2+) moieties via coordination through the terminal oxygen atoms, while in 2, the [Mn(2,2'-bipy)(3)](2+) ion balances the charge on the polyoxo anion without forming any covalent bond. To the best of our knowledge, this is the first example of transition metal-mediated transformation of [alpha-SiW9O34](10-) to [alpha-SiW12O40](4-).

A novel cation induced polymeric chain in Na-8[{Cu(gly)(2)}(2)]{H-2(H2W12O42)}] center dot 24H(2)O: hydrothermal synthesis, spectroscopic characterization and X-ray structure analysis

A novel bis(glycinato) copper(II) paradodecatungstate Na-8[{Cu(gly)(2)}(2)]-{H-2(H2W12O42)}] center dot 24H(2)O (1) has been synthesized under hydrothermal conditions. The crystal structure of 1 reveals an infinite one-dimensional chain along the [100] direction and is built from paradodecatungstate (H2W12O42)(10-) clusters joined through [Cu(gly)(2)] moieties. Parallel chains are interlinked by NaO6 octahedra to generate a two-dimensional network.

Efficiency and purity control in the preparation of pure and/or aluminum-doped barium ferrites by hydrothermal methods using ferrous ions as reactants

The synthesis of hexagonal barium ferrite (BaFe12O19) was studied under hydrothermal conditions by a method in which a significant amount of ferrous chloride was introduced along side ferric chloride among the starting materials. Though all of the Fe2+ ions in the starting material were converted to Fe3+ ions in the final product, Fe2+ was confirmed to participate differently from the Fe3+ used in the conventional method in the mechanism of forming barium ferrite. Indeed the efficiency of the synthesis and the quality of the product and the lack of impurities such as Fe2O3 and BaFe2O4 were improved when Fe2+ was included. However, the amount of ferrous ions that could be included to obtain the desired product was limited with an optimum ratio of 2:8 for FeCl2/FeCl3 when only 2h of reaction time were needed. It was also found that the role of trivalent Fe3+ could be successfully replaced by Al3+. Up to 50% of their on could be replaced by Al3+ in the reactants to produce Al- doped products. It was also found that the ratio of Fe2+/M3+ could be increased in the presence of Al3+ to produce high quality barium ferrite.

Purified phenolics from hydrothermal treatments of biomass: ability to protect sunflower bulk oil and model food emulsions from oxidation

The phenolic fractions released during hydrothermal treatment of selected feedstocks (corn cobs, eucalypt wood chips, almond shells, chestnut burs, and white grape pomace) were selectively recovered by extraction with ethyl acetate and washed with ethanol/water solutions. The crude extracts were purified by a relatively simple adsorption technique using a commercial polymeric, nonionic resin. Utilization of 96% ethanol as eluting agent resulted in 47.0-72.6% phenolic desorption, yielding refined products containing 49-60% w/w phenolics (corresponding to 30-58% enrichment with respect to the crude extracts). The refined extracts produced from grape pomace and from chestnut burs were suitable for protecting bulk oil and oil-in-water and water-in-oil emulsions. A synergistic action with bovine serum albumin in the emulsions was observed.

Hydrothermal synthesis of [C6H16N2][In2Se3(Se2)]: a new one-dimensional indium selenide

A new organically templated indium selenide, [C6H16N2][In2Se3(Se2)], has been prepared hydrothermally from the reaction of indium, selenium and trans-1,4-diaminocyclohexane in water at 170 °C. This material was characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis, UV–vis diffuse reflectance spectroscopy, FT-IR and elemental analysis. The compound crystallises in the monoclinic space group C2/c (a=12.0221(16) Å, b=11.2498(15) Å, c=12.8470(17) Å, β=110.514(6)°). The crystal structure of [C6H16N2][In2Se3(Se2)] contains anionic chains of stoichiometry [In2Se3(Se2)]2−, which are aligned parallel to the [1 0 1] direction, and separated by diprotonated trans-1,4-diaminocyclohexane cations. The [In2Se3(Se2)]2− chains, which consist of alternating four-membered [In2Se2] and five-membered [In2Se3] rings, contain perselenide (Se2)2− units. UV–vis diffuse reflectance spectroscopy indicates that [C6H16N2][In2Se3(Se2)] has a band gap of 2.23(1) eV

Pb-210-Ra-226 and Ra-228-Th-232 systematics in young arc lavas: implications for magma degassing and ascent rates

New data show that island arc rocks have (Pb-210/Ra-226)(o) ratios which range from as low as 0.24 up to 2.88. In contrast, (Ra-22S/Th-232) appears always within error of I suggesting that the large Ra-226-excesses observed in arc rocks were generated more than 30 years ago. This places a maximum estimate on melt ascent velocities of around 4000 m/year and provides further confidence that the Ra-226 excesses reflect deep (source) processes rather than shallow level alteration or seawater contamination. Conversely, partial melting must have occurred more than 30 years prior to eruption. The Pb-210 deficits are most readily explained by protracted magma degassing. Using published numerical models, the data suggest that degassing occurred continuously for periods up to several decades just prior to eruption but no link with eruption periodicity was found. Longer periods are required if degassing is discontinuous, less than 100% efficient or if magma is recharged or stored after degassing. The long durations suggest much of this degassing occurs at depth with implications for the formation of hydrothermal and copper-porphyry systems. A suite of lavas erupted in 1985-1986 from Sangeang Api volcano in the Sunda arc are characterised by deficits of Pb-210 relative to Ra-226 from which 6-8 years of continuous Rn-222 degassing would be inferred from recent numerical models. These data also form a linear (Pb-210)/Pb-(Ra-226)/Pb array which might be interpreted as a 71-year isochron. However, the array passes through the origin suggesting displacement downwards from the equiline in response to degassing and so the slope of the array is inferred not to have any age significance. Simple modelling shows that the range of (Ra-226)/Pb ratios requires thousands of years to develop consistent with differentiation occurring in response to cooling at the base of the crust. Thus, degassing post-dated, and was not responsible for magma differentiation. The formation, migration and extraction of gas bubbles must be extremely efficient in mafic magma whereas the higher viscosity of more siliceous magmas retards the process and can lead to Pb-210 excesses. A possible negative correlation between (Pb-210/Ra-226)(o) and SO2 emission rate requires further testing but may have implications for future eruptions. (C) 2004 Elsevier B.V. All rights reserved.

Pb-210-Ra-226 and Ra-228-Th-232 systematics in young arc lavas: implications for magma degassing and ascent rates

New data show that island arc rocks have (Pb-210/Ra-226)(o) ratios which range from as low as 0.24 up to 2.88. In contrast, (Ra-22S/Th-232) appears always within error of I suggesting that the large Ra-226-excesses observed in arc rocks were generated more than 30 years ago. This places a maximum estimate on melt ascent velocities of around 4000 m/year and provides further confidence that the Ra-226 excesses reflect deep (source) processes rather than shallow level alteration or seawater contamination. Conversely, partial melting must have occurred more than 30 years prior to eruption. The Pb-210 deficits are most readily explained by protracted magma degassing. Using published numerical models, the data suggest that degassing occurred continuously for periods up to several decades just prior to eruption but no link with eruption periodicity was found. Longer periods are required if degassing is discontinuous, less than 100% efficient or if magma is recharged or stored after degassing. The long durations suggest much of this degassing occurs at depth with implications for the formation of hydrothermal and copper-porphyry systems. A suite of lavas erupted in 1985-1986 from Sangeang Api volcano in the Sunda arc are characterised by deficits of Pb-210 relative to Ra-226 from which 6-8 years of continuous Rn-222 degassing would be inferred from recent numerical models. These data also form a linear (Pb-210)/Pb-(Ra-226)/Pb array which might be interpreted as a 71-year isochron. However, the array passes through the origin suggesting displacement downwards from the equiline in response to degassing and so the slope of the array is inferred not to have any age significance. Simple modelling shows that the range of (Ra-226)/Pb ratios requires thousands of years to develop consistent with differentiation occurring in response to cooling at the base of the crust. Thus, degassing post-dated, and was not responsible for magma differentiation. The formation, migration and extraction of gas bubbles must be extremely efficient in mafic magma whereas the higher viscosity of more siliceous magmas retards the process and can lead to Pb-210 excesses. A possible negative correlation between (Pb-210/Ra-226)(o) and SO2 emission rate requires further testing but may have implications for future eruptions. (C) 2004 Elsevier B.V. All rights reserved.

Carbon-decorated FePt nanoparticles

FePt magnetic nanoparticles are an important candidate material for many future magnetic applications. FePt exists as two main phases, that is, a disordered face-centered cubic (fcc) structure, which is generally prepared by chemical methods at low temperatures, and the high-temperature chemically ordered face-centered tetragonal (fct) structure. The fee FePt, with low coercivity but associated with superparamagnetic properties, may find applications as a magnetic fluid or as a nanoscale carrier for chemical or biochemical species in biomedical areas, while fct FePt is proposed for use in ultrahigh-density magnetic recording applications. However, for both of these applications an enhancement of the intrinsically weak magnetic properties, the avoidance of magnetic interferences from neighbor particles, and the improved stability of the small magnetic body remain key practical issues. We report a simple synthetic method for producing FePt nanoparticles that involves hydrothermal treatment of Fe and Pt precursors in glucose followed by calcination at 900 degrees C. This new method produces thermally stable spheroidal graphite nanoparticles (large and fullerene-like) that encapsulate or decorate FePt particles of ca. 5 nm with no severe macroscopic particle coalescence. Also, a low coercivity of the material is recorded; indicative of small magnetic interference from neighboring carbon-coated particles. Thus, this simple synthetic method involves the use of a more environmentally acceptable glucose/aqueous phase to offer a protective coating for FePt nanoparticles. It is also believed that such a synthetic protocol can be readily extended to the preparation of other graphite-coated magnetic iron alloys of controlled size, stoichiometry, and physical properties.

Synthesis, structure and magnetic characterisation of a new layered ammonium manganese(II) diphosphate hydrate, (NH4)(2)[Mn-3(P2O7)(2)(H2O)(2)]

A new layered ammonium manganese(II) diphosphate, (NH4)(2)[Mn-3(P2O7)(2)(H2O)(2)], has been synthesised under solvothermal conditions at 433 K in ethylene glycol and the structure determined at 293 K using single-crystal X-ray diffraction data (M-r = 584.82, monoclinic, space group P2(1)/a, a = 9.4610( 8), b = 8.3565( 7), c = 9.477(1) Angstrom, beta = 99.908(9) degrees, V = 738.07 Angstrom(3), Z = 2, R = 0.0351 and R-w = 0.0411 for 1262 observed data (I > 3(sigma(I))). The structure consists of chains of cis- and trans-edge sharing MnO6 octahedra linked via P2O7 units to form layers of formula [Mn3P4O14(H2O)(2)](2-) in the ab plane. Ammonium ions lie between the manganese-diphosphate layers. A network of interlayer and ammonium-layer based hydrogen bonding holds the structure together. Magnetic measurements indicate Curie - Weiss behaviour above 30 K with mu(eff) = 5.74(1) mu(B) and theta = -23(1) K, consistent with the presence of high-spin Mn2+ ions and antiferromagnetic interactions. However, the magnetic data reveal a spontaneous magnetisation at 5 K, indicating a canting of Mn2+ moments in the antiferromagnetic ground state. On heating (NH4)(2)[Mn-3(P2O7)(2)(H2O)(2)] in water at 433 K under hydrothermal conditions, Mn-5(HPO4)(2)(PO4)(2).4H(2)O, synthetic hureaulite, is formed.

Helices, chirality and interpenetration: the versatility and remarkable interconversion of silver-copper cyanide frameworks

The structural transformations between cesium silver-copper cyanides under modest conditions, both in solution and in the solid state, are described. Three new cesium silver(I) copper(I) cyanides with three-dimensional (3-D) framework structures were prepared as single crystals from a one-pot reaction initially heated under hydrothermal conditions. The first product to appear, Cs3Ag2Cu3(CN)(8) (I), when left in contact with the supernatant produced CsAgCu(CN)(3) (II) and CsAgCu(CN)(3)center dot 1/3H(2)O (III) over a few months via a series of thermodynamically controlled cascade reactions. Crystals of the hydrate (III) can be dehydrated to polycrystalline CsAgCu(CN)(3) (II) on heating at 100 degrees C in a remarkable solid-state transformation involving substantial breaking and reconnection of metal-cyanide linkages. Astonishingly, the conversion between the two known polymorphs of CsAg2Cu(CN)(4), which also involves a major change in connectivity and topology, occurs at 180 degrees C as a single-crystal to single-crystal transformation. Structural features of note in these materials include the presence of helical copper-cyanide chains in (I) and (II), which in the latter compound produce a chiral material. In (II) and (III), the silver-copper cyanide networks are both self- and interpenetrating, features also seen in the known polymorphs of CsAg2Cu(CN)(4).

Bending, twisting, and breaking CuCN chains to produce framework materials: the reactions of CuCN with alkali-metal halides

The reactions of the low-temperature polymorph of copper(I) cyanide (LT-CuCN) with concentrated aqueous alkali-metal halide solutions have been investigated. At room temperature, KX (X = Br and I) and CsX (X = Cl, Br, and I) produce the addition products K[Cu-2(CN)(2)Br](H2O)-H-. (I), K-3[Cu-6(CN)(6)I-3](.)2H(2)O (II), Cs[Cu-3(CN)(3)Cl] (III), Cs[Cu-3(CN)(3)Br] (IV), and Cs-2[Cu-4(CN)(4)I-2](H2O)-H-. (V), with 3-D frameworks in which the -(CuCN)- chains present in CuCN persist. No reaction occurs, however, with NaX (X = Cl, Br, I) or KCl. The addition compounds, I-V, reconvert to CuCN when washed. Both low- and high-temperature polymorphs of CuCN (LT- and HT-CuCN) are produced, except in the case of Cs[Cu-3(CN)(3)Cl] (III), which converts only to LT-CuCN. Heating similar AX-CuCN reaction mixtures under hydrothermal conditions at 453 K for 1 day produces single crystals of I-V suitable for structure determination. Under these more forcing conditions, reactions also occur with NaX (X = Cl, Br, I) and KCl. NaBr and KCl cause some conversion of LT-CuCN into HT-CuCN, while NaCl and NaI, respectively, react to form the mixed-valence Cu(I)/Cu(II) compounds [Cu-II(OH2)(4)][Cu-4(I)(CN)(6)], a known phase, and [Cu-II(OH2)(4)][Cu-4(I)(CN)(4)I-2] (VI), a 3-D framework, which contains infinite -(CuCN)- chains. After 3 days of heating under hydrothermal conditions, the reaction between KI and CuCN produces [Cu-II(OH2)(4)][Cu-2(I)(CN)I-2](2) (VII), in which the CuCN chains are broken into single Cu-CN-Cu units, which in turn are linked into chains via iodine atoms and then into layers via long Cu-C and Cu-Cu interactions.

The threading of [(CuCN)(2)(mu-4,4 '-bpy)] sheets by CuCN chains

Yellow (CuCN)(2)[(CuCN)(2)(mu-4,4'-bpy)], formed in the hydrothermal reaction of CuCN with 4,4'-bipyridine at 453 K, contains two types of infinite CuCN chains. One set of CuCN chains is linked by 4,4'-bpy ligands to form almost flat sheets of composition [(CuCN)(2)(mu-4,4'-bpy)]. Holes in these sheets are aligned to allow pairs of approximately linear, infinite -(CuCN)- chains to thread through them. The closest interatomic approach between copper atoms in the threading chains and host sheets (similar to2.74 Angstrom) does not appear to represent a significant covalent bond as it leads to only a small distortion of the -(CuCN)- chains from linearity The relationship of this material to the previously determined structures of the host [(CuCN)(2)(mu-4,4'-bpy)] sheets and (CuCN)(3)[(CuCN)(2)(mu-4,4'-bPY)](2), in which these sheets are threaded by single -(CuCN)- chains, is discussed.

Synthesis, structural analysis, and magnetic behaviour of three fumarate bridged coordination polymers: five-fold interpenetrated diamond-like net of Ni-II, sheets of Ni-II and Co-II

The hydrothermal reactions of Ni(NO3)(2).6H(2)O, disodium fumarate (fum) and 1,2-bis(4-pyridyl)ethane (bpe)/1,3-bis(4-pyridyl) propane (bpp) in aqueous-methanol medium yield one 3-D and one 2-D metal-organic hybrid material, [Ni(fum)(bpe)] (1) and [Ni(fum)(bpp)(H2O)] (2), respectively. Complex 1 possesses a novel unprecedented structure, the first example of an "unusual mode" of a five-fold distorted interpenetrated network with metal-ligand linkages where the four six-membered windows in each adamantane-type cage are different. The structural characterization of complex 2 evidences a buckled sheet where nickel ions are in a distorted octahedral geometry, with two carboxylic groups, one acting as a bis-chelate, the other as a bis-monodentate ligand. The metal ion completes the coordination sphere through one water molecule and two bpp nitrogens in cis position. Variable-temperature magnetic measurements of complexes 1 and 2 reveal the existence of very weak antiferromagnetic intramolecular interactions and/or the presence of single-ion zero field splitting (D) of isolated Ni-II ions in both the compounds. Experimentally, both the J parameters are close, comparable and very small. Considering zero-field splitting of Ni-II, the calculated D values are in agreement with values reported in the literature for Ni-II ions. Complex 3, [{Co(phen)}(2)(fum)(2)] (phen=1,10-phenanthroline) is obtained by diffusing methanolic solution of 1,10-phenanthroline on an aqueous layer of disodium fumarate and Co(NO3)(2).6H(2)O. It consists of dimeric Co-II(phen) units, doubly bridged by carboxylate groups in a distorted syn-syn fashion. These fumarate anions act as bis-chelates to form corrugated sheets. The 2D layer has a (4,4) topology, with the nodes represented by the centres of the dimers. The magnetic data were fitted ignoring the very weak coupling through the fumarate pathway and using a dimer model.

Macrocyclic amines as structure-directing agents for the synthesis of three-dimensional antimony-sulfide frameworks

A new family of antimony sulfides, incorporating the macrocyclic tetramine 1,4,8,11-tetraazacyclotetradecane ( cyclam), has been prepared by a hydrothermal method. [C10N4H26][Sb4S7] (1), [Ni(C10N4H24)][Sb4S7] (2), and [Co(C10N4H24)](x)[C10N4H26](1-x)[Sb4S7] (0.08 <= x <= 0.74) (3) have been characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetry, and analytical electron microscopy. All three materials possess the same novel three-dimensional Sb4S72- framework, constructed from layers of parallel arrays of Sb4S84- chains stacked at 90 to one another. In 1, doubly protonated macrocyclic cations reside in the channel structure of the antimonysulfide framework. In 2 and 3, the cyclam acts as a ligand, chelating the divalent transition- metal cation. Analytical and X-ray diffraction data indicate that the level of metal incorporation in 2 is effectively complete, whereas in 3, both metalated and nonmetalated forms of the macrocycle coexist within the structure.