Synthesis of CdSnO(3).3H(2)O nanocubes via ion exchange and their thermal decompositions to cadmium stannate

Uniform crystalline CdSnO3.3H2O nanocubes with a 28-35 nm edge length have been obtained via the ion-exchange reaction of Na2Sn(OH)6 in a CdSO4 aqueous solution, assisted by ultrasonic treatment. Precursor Na2Sn(OH)6 crystals were prepared via hydrothermal treatment in an ethanol/water solution. The formation of CdSnO3.3H2O nanocubes resulted from the strain during the ion-exchange process. The influences of reaction conditions, such as ion-exchange (ultrasonic treatment) duration, solvent constitutes, surfactant, and pH on the formation of CdSnO3.3H2O crystals were described. Crystalline CdSnO3 and Cd2SnO4 have been obtained by thermal treatment at 300 and 500 degrees C, respectively, for 5 h under an inert-gas protecting condition using CdSnO3.3H2O nanocubes as the precursor. The cube shape of CdSnO3.3H2O was sustained after thermal decomposition to CdSnO3.     

Ambient pressure syntheses of size-controlled corundum-type In2O3 nanocubes

Hydrolysis of In(O-iPr)3 by 10 molar excess of water at 90 degrees C in a surfactant/solvent mixture of oleylamine/oleic acid/trioctylamine provides very small nanoparticles (<5 nm in diameter) of In(O)(OH). Subsequent in situ thermolysis of the formed In(O)(OH) nanoparticles at 350 degrees C and ambient pressure produces monodisperse h-In2O3 nanocubes, which can form an extended two-dimensional array on a flat surface. The size of the In2O3 nanocubes (8, 10, and 12 nm) could be easily controlled by the simple change in the amounts of employed surfactants. The h-In2O3 nanocube samples show blue PL emissions at room temperature due to, presumably, systematic oxygen vacancy.     

Novel reactivity mode of hydroxamic acids: a metalla-pinner reaction

The reaction between the nitrile complex trans-[PtCl(4)(EtCN)(2)] and benzohydroxamic acids RC(6)H(4)C([double bond]O)NHOH (R = p-MeO, p-Me, H, p-Cl, o-HO) proceeds smoothly in CH(2)Cl(2) at approximately 45 degrees C for 2-3 h (sealed tube) or under focused 300 W microwave irradiation for approximately 15 min at 50 degrees C giving, after workup, good yields of the imino complexes [PtCl(4)[NH[double bond]C(Et)ON[double bond]C(OH)(C(6)H(4)R)](2)] which derived from a novel metalla-Pinner reaction. The complexes [PtCl(4)[NH[double bond]C(Et)ON[double bond]C(OH)(C(6)H(4)R)](2)] were characterized by elemental analyses (C, H, N), FAB mass spectrometry, and IR and (1)H and (13)C[(1)H] spectroscopies, and [PtCl(4)[NH[double bond]C(Et)ON[double bond]C(OH)(Ph)](2)] (as the bis-dimethyl sulfoxide solvate), by X-ray single-crystal diffraction. The latter disclosed its overall trans-configuration with the iminoacyl species in the hydroximic tautomeric form in E-configuration which is held by N[bond]H...N hydrogen bond between the imine [double bond]NH atom and the hydroximic N atom.     

Preparation of mesostructured barium sulfate with high surface area by dispersion method and its characterization

The spherical and cubic mesoporous BaSO(4) particles with high surface area were successfully produced via one-step process through precipitation reaction in aqueous solution of Ba(OH)(2) and H(2)SO(4) with ethylene glycol (n-HOCH(2)CH(2)OH) as a modifying agent. The BaSO(4) nanomaterial revealed that the high surface area and the mesoporous was stable up to 400 degrees C. Agglomerate mesoporous barium sulfate nanomaterials were obtained by the reaction of Ba(2+) and SO(2-)(4) with ethylene glycol aqueous solution. The ethylene glycol was used to control the BaSO(4) particle size and to modify the surface property of the particles produced from the precipitation. The dried and calcined mesoporous BaSO(4) nanomaterials were characterized by X-ray diffraction (XRD), BET surface area and N(2) adsorption-desorption isotherm, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared resonance (FTIR) and thermogravimetric analysis (TGA). The as-prepared mesoporous dried BaSO(4) possesses a high BET surface area of 91.56 m(2) g(-1), pore volume of 0.188 cm(3) g(-1) (P/P(0)=0.9849) and pore size of 8.22 nm. The SEM indicates that the morphology of BaSO(4) nanomaterial shows shell like particles up to 400 degrees C, after that there is drastically change in the material due to agglomeration. Synthesis of mesoporous BaSO(4) nanomaterial is of significant importance for both sulphuric acid decomposition and oxidation of methane to methanol.     

Ultralong cadmium hydroxide nanowires: synthesis, characterization, and transformation into CdO nanostrands

Ultralong Cd(OH)2 nanowires were fabricated by a hydrothermal method from Cd(CH3COO)2 x H2O (0.01 mol/L) and C6H12N4 (0.015 mol/L) aqueous solution at 95 degrees C for 16 h without using any templates and were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and high-resolution transmission electron microscopy (HRTEM). The length of the nanowires reached several micrometers, giving an aspect ratio of a few thousands. The formation mechanism of the nanowires is attributed to the oriented attachment of small particles. The growth method for the 1D nanostructure presented here offers an excellent tool for the design of other advanced materials with anisotropic properties. The Cd(OH)2 nanowires efficiently captured negatively charged dye, and the adsorbed dye molecules can be released after the addition of EDTA. The Cd(OH)2 nanowires as template compounds were further transformed into CdO semiconductor nanomaterials with similar morphology by calcination under 350 degrees C in air for 3 h.     

Prussian Blue Analogue Mn3[Co(CN)6]2·nH2O porous nanocubes: large-scale synthesis and their CO2 storage properties

Prussian Blue Analogue (PBA) Mn(3)[Co(CN)(6)](2)·nH(2)O porous nanocubes were successfully synthesized in high yield at room temperature in the presence of poly(vinylpyrrolidone) (PVP) and characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The effects of synthetic parameters such as surfactant, the ratio of different solvents on the morphology and size of the particles were investigated. The experimental results showed that poly(vinylpyrrolidone) (PVP) and solvent ethanol play critical roles in the formation of uniform porous nanocubes. N(2) adsorption properties indicated that the Mn(3)[Co(CN)(6)](2) porous nanocubes with an average diameter of 240 nm possessed a high surface area of 675 m(2) g(-1) with total volume of 0.354 cm(3) g(-1). Moreover, the porous nanocubes showed high CO(2) adsorption at room temperature and 1 bar of pressure. To our knowledge, this is the first report on the synthesis of Mn(3)[Co(CN)(6)](2) nanomaterials and their CO(2) adsorption applications at the nanoscale.     

Fabrication of CuO pricky microspheres with tunable size by a simple solution route

A simple aqueous solution route was introduced for the fabrication of CuO pricky microspheres (CPMs) using CuCl(2) x 2H(2)O, Na(2)(C(4)H(4)O(6)) x 3H(2)O and NaOH as starting materials. The CPMs were composed of compressed nanothorns exhibiting tapering feature with tip size of less than 10 nm, and the size of CPMs could be tuned from 100-200 nm to 4-6 microm. The effects of the molar ratios of tartrate anions and NaOH to Cu(2+) cations, reagent concentration, and reaction temperature on the products were investigated, showing that the morphology of CPMs was determined by the molar ratio of tartrate to Cu(2+) cations and the size was greatly affected by reagent concentration and the molar ratio of NaOH to Cu(2+) cations in the precursor solution. The fabrication of CPMs went through rapid nucleation of Cu(OH)(2), aggregation and in situ dehydration of Cu(OH)(2), oriented-aggregation-based growth, and normal crystal growth of CuO nanothorns. The nucleation and crystal growth were successfully separated by controlled releasing of Cu(2+) and OH(-) ions through the reversible reaction of Cu(2+) cations, OH(-), and C(4)H(4)O(6)(2-) anions.     

Hydrothermal preparation of boehmite nanorods by selective adsorption of sulfate

A facile hydrothermal method was developed to synthesize boehmite nanorods with a length of 50-2000 nm, a diameter of 6-20 nm, and a preferential growth along [100] by treating the Al(OH)(3) gel in acidified sulfate solutions at 240 degrees C. Studies on the hydrothermal treatment of Al(OH)(3) gel in sulfate solutions showed that the morphology and the composition of the hydrothermal products were connected with the sulfate concentration and the pH of the hydrothermal solution. The aspect ratio of the boehmite nanorods increased to 300 as the initial H(2)SO(4) concentration increased to 0.043 mol x L(-1), whereas boehmite nanorods and (H(3)O)Al(3)(SO(4))(2)(OH)(6) cubic particles coexisted in the case of the initial H(2)SO(4) concentration > or = 0.054 mol x L (-1). Sole boehmite nanoflakes with a diameter of about 50 nm were formed under alkaline conditions (pH 10.5) despite the existence of the sulfate. The chemical and Raman analyses indicated that SO(4)(2-) in acidified solutions adsorbed on the boehmite surface via H-bonds. On the basis of the above results, the growth of boehmite along the [100] direction was attributed to the selective adsorption of SO(4) (2-) on the (010) and (001) planes of boehmite.     

Hydride reduction of NAD+ analogues by isopropyl alcohol: kinetics, deuterium isotope effects and mechanism

Observed pseudo-first-order rate constants (k(obs)) of the hydride-transfer reactions from isopropyl alcohol (i-PrOH) to two NAD(+) analogues, 9-phenylxanthylium ion (PhXn(+)) and 10-methylacridinium ion (MA(+)), were determined at temperatures ranging from 49 to 82 degrees C in i-PrOH containing various amounts of AN or water. Formations of the alcohol-cation ether adducts (ROPr-i) were observed as side equilibria. The equilibrium constants for the conversion of PhXn(+) to PhXnOPr-i in i-PrOH/AN (v/v = 1) were determined, and the equilibrium isotope effect (EIE = K(i-PrOH)/K(i-PrOD)) at 62 degrees C was calculated to be 2.67. The k(H) of the hydride-transfer step for both reactions were calculated on the basis of the k(obs) and K. The corresponding deuterium kinetic isotope effects (e.g., KIE(OD)(H) = k(H)(i-PrOH)/k(H)(i-PrOD) and KIE(beta-D6)(H) = k(obs)(i-PrOH)/k(obs)((CD3)2CHOH)), as well as the activation parameters, were derived. For the reaction of PhXn(+) (62 degrees C) and MA(+) (67 degrees C), primary KIE(alpha-D)(H) (4.4 and 2.1, respectively) as well as secondary KIE(OD)(H) (1.07 and 1.18) and KIE(beta-D6)(H) (1.1 and 1.5) were observed. The observed EIE and KIE(OD)(H) were explained in terms of the fractionation factors for deuterium between OH and OH(+)(OH(delta+)) sites. The observed inverse kinetic solvent isotope effect for the reaction of PhXn(+) (k(obs)(i-PrOH)/k(obs)(i-PrOD) = 0.39) is consistent with the intermolecular hydride-transfer mechanism. The dramatic reduction of the reaction rate for MA(+), when the water or i-PrOH cosolvent was replaced by AN, suggests that the hydride-transfer T.S. is stabilized by H-bonding between O of the solvent OH and the substrate alcohol OH(delta+). This result suggests an H-bonding stabilization effect on the T.S. of the alcohol dehydrogenase reactions.     

In(OH)3 and In2O3 nanorod bundles and spheres: microemulsion-mediated hydrothermal synthesis and luminescence properties

Indium hydroxide, In(OH)3, nano-microstructures with two kinds of morphology, nanorod bundles (around 500 nm in length and 200 nm in diameter) and caddice spherelike agglomerates (around 750-1000 nm in diameter), were successfully prepared by the cetyltrimethylammonium bromide (CTAB)/water/cyclohexane/n-pentanol microemulsion-mediated hydrothermal process. Calcination of the In(OH)3 crystals with different morphologies (nanorod bundles and spheres) at 600 degrees C in air yielded In2O3 crystals with the same morphology. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. The pH values of microemulsion play an important role in the morphological control of the as-formed In(OH)3 nano-microstructures from the hydrothermal process. The formation mechanisms for the In(OH)3 nano-microstructures have been proposed on an aggregation mechanism. In2O3 nanorod bundles and spheres show a similar blue emission peaking around 416 and 439 nm under the 383-nm UV excitation, which is mainly attributed to the oxygen vacancies in the In2O3 nano-microstructures.     

Generation and reactivity of rhodium(IV) complexes in aqueous solutions

At pH = 1 and 25 degrees C, the Fenton-like reactions of Fe(aq)(2+) with hydroperoxorhodium complexes LRh(III)OOH(2+) (L = (H(2)O)(NH(3))(4), k = 30 M(-1) s(-1), and L = L(2) = (H(2)O)(meso-Me(6)-[14]aneN(4)), k = 31 M(-1) s(-1)) generate short-lived, reactive intermediates, believed to be the rhodium(IV) species LRh(IV)O(2+). In the rapid follow-up steps, these transients oxidize Fe(aq)(2+), and the overall reaction has the standard 2:1 [Fe(aq)(2+)]/[LRhOOH(2+)] stoichiometry. Added substrates, such as alcohols, aldehydes, and (NH(3))(4)(H(2)O)RhH(2+), compete with Fe(aq)(2+) for LRh(IV)O(2+), causing the stoichiometry to change to <2:1. Such competition data were used to determine relative reactivities of (NH(3))(4)RhO(2+) toward CH(3)OH (1), CD(3)OH (0.2), C(2)H(5)OH (2.7), 2-C(3)H(7)OH (3.4), 2-C(3)D(7)OH (1.0), CH(2)O (12.5), C(2)H(5)CHO (45), and (NH(3))(4)RhH(2+) (125). The kinetics and products suggest hydrogen atom abstraction for (NH(3))(4)RhO(2+)/alcohol reactions. A short chain reaction observed with C(2)H(5)CHO is consistent with both hydrogen atom and hydride transfer. The rate constant for the reaction between Tl(aq)(III) and L(2)Rh(2+) is 2.25 x 10(5) M(-1) s(-1).     

Mononuclear nickel(III) complexes [Ni(III)(OR)(P(C6H3-3-SiMe3-2-S)3)](-) (R = Me, Ph) containing the terminal alkoxide ligand: relevance to the nickel site of oxidized-form [NiFe] hydrogenases

The unprecedented nickel(III) thiolate [Ni (III)(OR)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) [R = Ph ( 1), Me ( 3)] containing the terminal Ni (III)-OR bond, characterized by UV-vis, electron paramagnetic resonance, cyclic voltammetry, and single-crystal X-ray diffraction, were isolated from the reaction of [Ni (III)(Cl)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) with 3 equiv of [Na][OPh] in tetrahydrofuran (THF)-CH 3CN and the reaction of complex 1 with 1 equiv of [Bu 4N][OMe] in THF-CH 3OH, respectively. Interestingly, the addition of complex 1 into the THF-CH 3OH solution of [Me 4N][OH] also yielded complex 3. In contrast to the inertness of complex [Ni (III)(Cl)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) toward 1 equiv of [Na][OPh], the addition of 1 equiv of [Na][OMe] into a THF-CH 3CN solution of [Ni (III)(Cl)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) yielded the known [Ni (III)(CH 2CN)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) ( 4). At 77 K, complexes 1 and 3 exhibit a rhombic signal with g values of 2.31, 2.09, and 2.00 and of 2.28, 2.04, and 2.00, respectively, the characteristic g values of the known trigonal-bipyramidal Ni (III) [Ni (III)(L)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) (L = SePh, SEt, Cl) complexes. Compared to complexes [Ni (III)(EPh)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) [E = S ( 2), Se] dominated by one intense absorption band at 592 and 590 nm, respectively, the electronic spectrum of complex 1 coordinated by the less electron-donating phenoxide ligand displays a red shift to 603 nm. In a comparison of the Ni (III)-OMe bond length of 1.885(2) A found in complex 3, the longer Ni (III)-OPh bond distance of 1.910(3) A found in complex 1 may be attributed to the absence of sigma and pi donation from the [OPh]-coordinated ligand to the Ni (III) center.     

Controlled synthesis of high-quality PbS star-shaped dendrites, multipods, truncated nanocubes, and nanocubes and their shape evolution process

Well-defined single-crystalline PbS nano- and microstructures including dendrites, multipods, truncated nanocubes, and nanocubes were synthesized in high yield by a simple solution route. Novel star-shaped PbS dendrites with six symmetric arms along the 100 direction, each of which shows one trunk (long axis) and four branches (short axes), have been achieved using Pb(AC)2 and thioacetamide (TAA) as precursors, under the molar ratio Pb(AC)2/TAA = 2/1, at initial reaction temperature 80 degrees C, refluxing for 30 min at 100 degrees C, in the presence of cetyltrimethylammonium bromine (CTAB). The "nanorods" in each branch are parallel to each other in the same plane and are perpendicular to the trunk. The truncated nanocubes mainly bounded by the {100} plane were prepared under a different Pb(AC)2/TAA molar ratio, at initial reaction temperature 40 degrees C, refluxing for 12 h at 100 degrees C. Based on the systematic studies on their shape evolution, a possible growth mechanism of these PbS nano- and microstructures was proposed. The shapes of PbS nanocrystals with face-centered cubic (fcc) structure are mainly determined by the ratio (R) between the growth rates along the (100) and (111) directions. The Pb(AC)2/TAA molar ratio and the initial reaction temperature influence the growth ratio R in the formation of PbS nuclei at an early stage, which results in the final morphology of PbS nanocrystals. Under the current experimental conditions, we can control the PbS shape evolution by simply tuning the molar ratio, the initial reaction temperature, and the period of reaction. Based on the systematic studies on the shape evolution, this approach is expected to be employed for the control-shaped synthesis of other fcc structural semiconductor nanomaterials. The photoluminescence properties were investigated and the prepared nano- and microstructures displayed a very strong luminescence around 600-650 nm at room temperature.     

Synthesis, characterization, and photoluminescence property of LaCO3OH microspheres

Novel LaCO3OH microspheres with the hexagonal phase were synthesized by a hydrothermal method using La(NO3)(3).6H2O and urea CO(NH2)2 as the starting materials. Various experimental parameters were examined, such as the reaction temperature, the reaction time, and the molar ratios of the starting reagents. The as-synthesized products were characterized by powder X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and photoluminescence (PL). The PL result showed one broad emission band centered at 438 nm (lambdaex=365 nm) of the pure LaCO3OH microspheres. In addition, a possible formation mechanism of LaCO3OH microspheres and the PL property of pure LaCO3OH microspheres were discussed.     

Chemistry at corners and edges: generation and adsorption of H atoms on the surface of MgO nanocubes

We used UV light to generate site-selective O- hole centers at three-coordinated corner oxygen sites on MgO nanocubes. These highly reactive O- radicals split H2 homolytically and, in the course of this reaction, become hydroxylated and produce hydrogen atoms. The hydrogen atoms adsorb predominantly at cube edges and dissociate into surface-trapped electrons and protons. We propose that the experimentally observed (H+)(e-) centers are formed adjacent to the hydroxyl groups generated in the homolytic splitting process and can be defined as (H+)3C...(e-)(H+)NC centers where 3C and NC refer to the coordination numbers of the corresponding hydroxylated oxygen sites. Our ab initio embedded cluster calculations reveal that the electronic properties of (H+)3C...(e-)(H+)4C centers situated along MgO nanocube edges are consistent with both the electron-paramagnetic-resonance signal parameters and the reported optical-absorption properties. The transformation of corner O- centers into the (H+)3C...(e-)(H+)NC-type centers prevents their recombination with electronic surface centers and, hence, significantly alters the electronic structure of MgO nanocubes by introducing shallow electron traps.     

One-pot synthesis of ZnS/polymer composites in supercritical CO2-ethanol solution and their applications in degradation of dyes

A facile method to decorate the polymeric hollow spheres with ZnS nanoparticles has been presented. In this method, the precursors, Zn(Ac)(2)H(2)O and CH(3)CSNH(2), were first adsorbed by the polymer substrate in supercritical CO(2)-ethanol solution at 35 degrees C. Followed by heating the mixture at 100 degrees C for 2 h, ZnS/polymer composites were obtained. The as-produced ZnS/polymer composites were characterized by means of IR spectra, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy. It was demonstrated that crystalline ZnS nanoparticles with size of 3-5 nm were uniformly decorated on the polymer spheres under suitable conditions. The resultant ZnS/polymer composites exhibited high efficiency for degrading eosin B, methyl orange and methylene blue under UV light irradiation.     

Oxidation Kinetics of the Potent Insulin Mimetic Agent Bis(maltolato)oxovanadium(IV) (BMOV) in Water and in Methanol

The kinetics of oxidation of bis(maltolato)oxovanadium(IV), BMOV or VO(ma)(2), by dioxygen have been studied by UV-vis spectroscopy in both MeOH and H(2)O media. The VO(ma)(2):O(2) stoichiometry was 4:1. In aqueous solution, the pH-dependent rate of the VO(ma)(2)/O(2) reaction to generate cis-[VO(2)(ma)(2)](-) is attributed to the deprotonation of coordinated H(2)O, the deprotonated species [VO(ma)(2)(OH)](-) being more easily oxidized (k(OH) = 0.39 M(-)(1) s(-)(1), 25 degrees C) than the neutral form VO(ma)(2)(H(2)O) (k(H)()2(O) = 0.08 M(-)(1) s(-)(1), 25 degrees C). The activation parameters for the two second-order reactions in aqueous solution were deduced from variable temperature kinetic measurements. In MeOH, VO(ma)(2) was oxidized by dioxygen to cis-VO(OMe)(ma)(2), whose structure was characterized by single-crystal X-ray diffraction; the crystals were monoclinic, C2/c, with a = 28.103(1) ?, b = 7.721(2) ?, c = 13.443(2) ?, beta = 94.290(7) degrees, and Z = 8. The structure was solved by Patterson methods and was refined by full-matrix least-squares procedures to R = 0.043 for 1855 reflections with I >/= 3sigma(I). The kinetic results are consistent with a mechanism involving an attack of O(2) at the V(IV) center, followed by the formation of radicals and H(2)O(2) as transient intermediates.     

Facile in situ synthesis of nanofluids based on ionic liquids and copper oxide clusters and nanoparticles

Two stable nanofluids comprising of mixed valent copper(I,II) oxide clusters (<1 nm) suspended in 1-butyl-3-methylimidazolium acetate, [C(4)mim][OAc], and copper(II) oxide nanoparticles (<50 nm) suspended in trioctyl(dodecyl)phosphonium acetate, [P(8 8 8 12)][OAc], were synthesised in a facile one-pot reaction from solutions of copper(II) acetate hydrate in the corresponding ionic liquids. Formation of the nanostructures was studied using (13)C NMR spectroscopy and differential scanning calorimetry (DSC). From a solution of Cu(OAc)(2) in 1-ethyl-3-methylimidazolium acetate, [C(2)mim][OAc], crystals were obtained that revealed the structure of [C(2)mim][Cu(3)(OAc)(5)(OH)(2)(H(2)O)]·H(2)O, indicating the formation of copper hydroxo-clusters in the course of the reaction. Synthesised nanostructures were studied using transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Physical properties of the prepared IL-nanofluids were examined using IR and UV-VIS spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and densitometry.     

Single‐microemulsion‐based Hydrothermal Approach to In(OH)3 and In2O3 Nanocubes

Well‐defined indium hydroxide [In(OH)₃] nanocubes have been successfully prepared through a facile single‐microemulsion‐mediated hydrothermal process at a relatively low temperature. Calcination of the In(OH)₃ precursor at 400°C in a furnace yielded In₂O₃ crystals with the same morphology. X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), and transmission electron microscopy (TEM) were used to characterize the samples. The effects of reaction parameters on the formation of nanostructures were also discussed, and the nucleation, aggregation and anisotropic growth mechanism was proposed. Room temperature photoluminescence (PL) spectra as well as the ultraviolet‐visible (UV‐vis) absorbance spectra were carried out on the In₂O₃ crystals to investigate their optical properties.     

Copper and Bismuth Complexes Containing Dipyridyl gem-Diolato Ligands: Bi(III)(2)[(2-Py)(2)CO(OH)](2)(O(2)CCF(3))(4)(THF)(2), Cu(II)[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), and Cu(II)(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), a Ferromagnetically Coupled Tetranuclear Copper(II) Chain

The reactions of the singly deprotonated di-2-pyridylmethanediol ligand (dpmdH(-)) with copper(II) and bismuth(III) have been investigated. A new dinuclear bismuth(III) complex Bi(2)(dpmdH)(2)(O(2)CCF(3))(4)(THF)(2), 1, has been obtained by the reaction of BiPh(3) with di-2-pyridyl ketone in the presence of HO(2)CCF(3) in tetrahydrofuran (THF). The reaction of Cu(OCH(3))(2) with di-2-pyridyl ketone, H(2)O, and acetic acid in a 1:2:2:2 ratio yielded a mononuclear complex Cu[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), 2, while the reaction of Cu(OAC)(2)(H(2)O) with di-2-pyridyl ketone and acetic acid in a 2:1:1 ratio yielded a tetranuclear complex Cu(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), 3. The structures of these complexes were determined by single-crystal X-ray diffraction analyses. Three different bonding modes of the dpmdH(-) ligand were observed in compounds 1-3. In 2, the dpmdH(-) ligand functions as a tridentate chelate to the copper center and forms a hydrogen bond between the OH group and the noncoordinating HO(2)CCH(3) molecule. In 1 and 3, the dpmdH(-) ligand functions as a bridging ligand to two metal centers through the oxygen atom. The two pyridyl groups of the dpmdH(-) ligand are bound to one bismuth(III) center in 1, while in 3 they are bound two copper(II) centers, respectively. Compound 3 has an unusual one dimensional hydrogen bonded extended structure. The intramolecular magnetic interaction in 3 has been found to be dominated by ferromagnetism. Crystal data: 1, C(38)H(34)N(4)O(14)F(12)Bi(2), triclinic P&onemacr;, a = 11.764(3) ?, b = 11.949(3) ?, c = 9.737(1) ?, alpha =101.36(2) degrees, beta = 105.64(2) degrees, gamma = 63.79(2) degrees, Z = 1; 2, C(26)H(26)N(4)O(8)Cu/CH(2)Cl(2), monoclinic C2/c, a = 25.51(3) ?, b = 7.861(7) ?, c = 16.24(2) ?, beta = 113.08(9) degrees, Z = 4; 3, C(34)H(40)N(4)O(18)Cu(4)/CH(2)Cl(2), triclinic P&onemacr;, a = 10.494(2) ?, b = 13.885(2) ?, c = 7.900(4) ?, alpha =106.52(2) degrees, beta = 90.85(3) degrees, gamma = 94.12(1) degrees, Z = 1.