Cu[(PPh3)2O](acac): Cu charge-compensated by a coordinating acac anion

A complex Cu[(PPh₃)₂O](acac)[(PPh₃)₂O = Bis(2-diphenyl-phosphinophenyl) ether; acac = acetylacetone] was obtained by solution reactions and structurally characterized. The title complex is characterized by an isolated structure. X-ray structure analysis of the title complex shows that acac and (PPh₃)₂O behave as chelating ligands. Photoluminescent investigation reveals that the title complex displays a strong blue-light emission.     

Synthesis, characterization and crystal structure of cis,mer-[ReH(CO)2{PPh(OMe)2}3]

The dicarbonylhydride complex cis,mer-[ReH(CO)₂{PPh(OMe)₂}₃] (1) was serendipitously obtained when, in an attempt to replace a CO ligand by the phosphonite ligand PPh(OMe)₂ in [ReH(CO)₃(L)] (L = PPh₂OCH₂CH₂OPPh₂), this complex was treated with PPh(OMe)₂ under UV irradiation. The complex 1 was characterized by IR, ¹H and ³¹P{¹H} NMR spectroscopy and by crystal structure determination. The spectroscopic features are consequent with the cis,mer configuration showed by the X-ray crystallographic analysis of the complex. The environment of the metal centre is a distorted octahedron.     

Synthesis, structure and photoluminescence of a novel palladium(I) compound: [Pd3(μ3-Cl)2(dppp)3][Pd2(μ2-Cl)3(PPh3)2](PPh3)2

Pd(PPh₃)₂Cl₂ reacts with PdCl₂ and 1,3-bis(diphenylphosphine)propane (dppp) in ethanol–DMF–pyridine mixed solvent to yield a novel palladium(I) compound [Pd₃(μ₃-Cl)₂(dppp)₃][Pd₂(μ₂-Cl)₃(PPh₃)₂](PPh₃)₂. It features an isolated structure based on [Pd₃(μ₃-Cl)₂(dppp)₃]⁺ cations having triangulo-palladium clusters and [Pd₂(μ₂-Cl)₃(PPh₃)₂]⁻ anions in which the coordination environment of palladium is an unusual tetrahedral geometry. Its photoluminescence is measured.     

Synthesis and H2 uptake of Cu2(OH)3Cl, Cu(OH)2 and CuO nanocrystal aggregate

Monodispersed Cu₂(OH)₃Cl nanoplatelets, Cu(OH)₂ nanowires, CuO nanoparticles and nanoribbons with a spherical morphology were synthesized using hydrothermal and heat-treatment reactions, and their H₂ storage characteristics were examined. The Cu₂(OH)₃Cl nanoplatelets particles formed immediately after mixing the reactant, which subsequently formed larger uniform spherical particles in the submicron range. This procedure highlights a practical strategy for producing spherical Cu(OH)₂ and CuO materials consisting of monodispersed nanocrystals. The spherical aggregates of Cu₂(OH)₃Cl nanoplatelets heat-treated at 473 K could reversibly store up to 2.35 wt.% H₂ at 38 bar and 293 K.     

Synthesis and molecular structure of the sodium arsanediyl zincate [(thf)Na]2[(EtZn)6(AsSiiPr3)4]

The reaction of NaAs(H)SiiPr₃ with ZnEt₂ in the presence of additional triisopropylsilylarsane yields the heterobimetallic complex [(thf)Na]₂ [(EtZn)₆(AsSiiPr₃)₄] (1) in the shape of red prisms. The Na–As and Zn–As bond lengths show values of 301/309 pm and between 247 and 260 pm, respectively.     

The metal-chain complexes (X)[Os(CO)3(CNBu)]3Mn(CO)5 (X=Cl, Br, I)

In what is a new metal-chain forming reaction, (X)[Os(CO)₃(CNBu^t)]₃Mn(CO)₅ (X=Cl, Br, I) complexes have been prepared by the successive addition of Os(CO)₄(CNBu^t) to Mn(CO)₅(X) in hexane. The crystal structure of the iodo derivative reveals it to contain an approximately linear Os₃ Mn chain of metal atoms.     

Synthesis and characterisation of tetraosmium carbonyl clusters bearing an azo type ligand: crystal and molecular structures of [Os4(μ-H)4(CO)11(NC5H4N=NPh)] and [Os4(μ-H)4(CO)10(MeCN)(NC5H4N=NPh)]

Reaction of [Os₄(μ-H)₄(CO)₁₀(MeCN)₂] with one equivalent of 4-phenylazopyridine (4-PAP) in CH₂Cl₂ at ambient conditions afforded two new tetraosmium clusters [Os₄(μ-H)₄(CO)₁₁(NC₅H₄N=NPh)] (1) and [Os₄(μ-H)₄(CO)₁₀(MeCN)(NC₅H₄N=NPh)] (2) in moderate yields. Compound 1 exists as a pair of isomers in solution, which differ in the location of the bridging hydride ligands. The molecular structures of clusters 1 and 2 consist of a highly distorted tetrahedral metal skeleton, with the azo ligand terminally bonded to an osmium atom.     

Hydrothermal synthesis and crystal structure of a novel cyanide-bridged double helical copper(I) coordination polymer [Cu3(CN)3(phen)]n

Hydrothermal reaction of CuCN, K₃[Fe(CN)₆] and 1,10-phenanthroline affords a novel cyanide-bridged copper(I) coordination polymer [Cu₃(CN)₃(phen)]_n (1). The complex displays an interesting one-dimensional neutral double helical framework with (phen)Cu–CN– side-arms as interchain bridges. The double helical chains are close packed in a parallel fashion, and the phen ligands stack in an interpenetrating mode, which leads to π–π interactions between parallel phen planes. The thermal stability and fluorescent property have also been investigated.     

Synthesis and photoluminescence enhancement of Ca3Sr3(VO4)4:Eu3+ red phosphors by co-doping with La3+

In this study, a series of red-emitting Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphors co-doped with La³⁺ was prepared using the combustion method. The microstructures, morphologies, and photoluminescence properties of the phosphors were investigated. All Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ samples synthesized at temperatures greater than 700 ℃ exhibited the same standard rhombohedral structure of Ca₃Sr₃(VO₄)₄. Furthermore, the Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ phosphor was effectively excited by near-ultraviolet light of 393 nm and blue light of 464 nm. The strong excitation peak at 464 nm corresponded to the ⁷F₀→⁵D₂ electron transition of Eu³⁺. The strong emission peak observed at 619 nm corresponded to the ⁵D₀→⁷F₂ electron transition of Eu³⁺. Co-doping with La³⁺ significantly improved the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺ red phosphors. The optimum luminescence of the phosphor was observed at Eu³⁺ and La³⁺ concentrations of 5% and 6%, respectively. Moreover, co-doping with La³⁺ also improved the fluorescence lifetime and thermal stability of the Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphor. The CIE chromaticity coordinate of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ was closer to the NTSC standard for red phosphors than those of other commercial phosphors; moreover, it had greater color purity than that of all the samples tested. The red emission intensity of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ at 619 nm was ~1.53 times that of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺ and 2.63 times that of SrS:Eu²⁺. The introduction of charge compensators could further increase the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ red phosphors. The phosphors synthesized herein are promising red-emitting phosphors for applications in white light-emitting diodes under irradiation by blue chips.     

Ionic conductivity of PEO9: Cu(CF3SO3)2: Al2O3 nano-composite solid polymer electrolyte

Cu⁺⁺ ion containing solid polymer electrolytes exhibit interesting electrochemical properties. In particular, the polymer electrolyte PEO₉:Cu(CF₃SO₃)₂ made by complexing copper triflate (CuTf₂) with PEO appears to show scientifically intriguing transport properties. Although some copper ion transport in these systems has been seen from plating stripping processes, the detailed mechanism of ionic transport and the species involved are yet to be established. In order to obtain enhanced ionic conductivities and also to contribute towards understanding the ionic transport process in Cu⁺⁺ ion containing, PEO based composite polymer electrolytes, we have studied the system PEO₉: CuTf₂: Al₂O₃ incorporating 10 wt.% of alumina filler particles of grain size 10 μm, 37 nm, 10–20 nm and also particles of pore size 5.8 nm. Thermal and electrical measurements show that the system remains amorphous down to room temperature. The composite electrolyte is predominantly an ionic conductor with electronic conductivity less than 2%. The triflate (CF₃SO₃⁻) anions appear to be the dominant carriers. The presence of alumina grains has enhanced the conductivity significantly from room temperature up to 100 °C. The nano-porous grains with 5.8 nm pore size and 150 m²/g specific surface area exhibited the maximum conductivity enhancement. This enhancement has been attributed to Lewis acid–base type surface interactions of ionic species with O²⁻ and OH⁻ groups on the filler grain surface.     

四元混配配合物[Ln(x-MBA)2(NO3)(Phen)]2的合成及表征

在酸性介质,乙醇/水混合溶剂中合成得到了三个系列的四元混配配合物[Ln(x-MBA)2(NO3)(Phen)]2(Ln=La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Er;MBA=CH3C6H4COO-).用元素分析、IR、UV、DTA-TG和1HNMR等方法对配合物进行了表征,测量了三个Eu配合物的荧光光谱和三个Gd配合物的ESR谱.     

Facile Synthesis of Amine-Functionalized Eu3+-Doped La(OH)3 Nanophosphors for Bioimaging

Here, we report a straightforward synthesis process to produce colloidal Eu³⁺-activated nanophosphors (NPs) for use as bioimaging probes. In this procedure, poly(ethylene glycol) serves as a high-boiling point solvent allowing for nanoscale particle formation as well as a convenient medium for solvent exchange and subsequent surface modification. The La(OH)₃:Eu³⁺ NPs produced by this process were ~3.5 nm in diameter as determined by transmission electron microscopy. The NP surface was coated with aminopropyltriethoxysilane to provide chemical functionality for attachment of biological ligands, improve chemical stability and prevent surface quenching of luminescent centers. Photoluminescence spectroscopy of the NPs displayed emission peaks at 597 and 615 nm (λ_ex = 280 nm). The red emission, due to ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ transitions, was linear with concentration as observed by imaging with a conventional bioimaging system. To demonstrate the feasibility of these NPs to serve as optical probes in biological applications, an in vitro experiment was performed with HeLa cells. NP emission was observed in the cells by fluorescence microscopy. In addition, the NPs displayed no cytotoxicity over the course of a 48-h MTT cell viability assay. These results suggest that La(OH)₃:Eu³⁺ NPs possess the potential to serve as a luminescent bioimaging probe.     

Phase composition,Raman spectra,infrared spectra and dielectric properties of Li2MgTi1-x(Mg1/3Nb2/3)xO4 ceramics at microwave frequency

The Li₂MgTi_1-x(Mg_1/3Nb_2/3)_xO₄ (0?≤x?≤?0.5) ceramics were prepared by the conventional solid-state method. The relationship among phase composition, substitution amount and microwave dielectric properties of the ceramics was symmetrically investigated. All the samples possess the rock salt structure with the space group of Fm-3m. As the x value increases from 0 to 0.5, the dielectric constant linearly decreases from 16.75 to 15.56, which can be explained by the variation of Raman spectra and infrared spectra. The Q·f value shows an upward tendency in the range of 0?≤x?≤?0.3, but it then decreases when x?>?0.3. In addition, the temperature coefficient of resonant frequency (τ_f) is shifted toward zero with the increasing (Mg_1/3Nb_2/3)⁴⁺ addition. By comparison, the Li₂MgTi_0.7(Mg_1/3Nb_2/3)_0.3O₄ ceramics sintered at 1400?°C can achieve an excellent combination of microwave dielectric properties: ε_r=?16.19, Q·f =?160,000?GHz and τ_f =??3.14?ppm/°C.     

Synthesis and spectroscopic investigation of the pyrazole complexes. The X-ray structure of [ReOBr3(OAsPh3)(pzH)]

The [ReOX₃(OAsPh₃)(AsPh₃)] complexes react with pyrazole in dry tetrahudrofuran to give new monomeric oxo rhenium(V) complexes – [ReOX₃(OAsPh₃)(pzH)]. This paper presents synthesis and spectroscopic characterisation of [ReOX₃(OAsPh₃)(pzH)] compounds and X-ray structure of the bromine analogue.     

Synthesis, crystal structure and thermal stability of tetrahydroborate sodalite Na8[AlSiO4]6(BH4)2

Tetrahydroborate sodalite formation was investigated in the system Na₂O–SiO₂–Al₂O₃–NaBH₄–H₂O under mild hydrothermal conditions. Due to the high degree of decomposition of hydroborates in aqueous solutions synthesis conditions were tuned by variation of the parameters alkalinity, liquid/solid ratio, reaction temperature and reaction time. The insertion of 8–16 molar NaOH solution was crucial for the higher stability of pure tetrahydroborate salt under strong alkaline conditions. Synthesis at 393 K and 24 h reaction time reveal tetrahydroborate sodalite Na₈[AlSiO₄]₆(BH₄)₂ beside a small amount of amorphous material within the total batch. Structure, composition and thermal stability of this new sodalite was investigated using XRD, NMR, infrared and TG/DTA methods. The crystal structure of tetrahydroborate sodalite has been refined in the space group P-43n with a = 891.61(2) pm. The Si- and Al-atoms of the aluminosilicate framework are completely ordered. The boron atoms of the tetrahydroborate anions are located at the centre of the sodalite cage whereas the hydrogen atoms are positionally disordered. Na₈[AlSiO₄]₆(BH₄)₂ shows a high stability under inert gas conditions. At atmospheric conditions the group can be oxidized to borate and boroxide anions suggesting the formation of hydrogen which leaves the sodalite cages. Future investigation of reloading properties of the oxidized form could be highly interesting for the hydrogen storage capabilities of these sodalites.     

Mild oxidation of alcohols with periodic acid catalyzed by [Ru(acac)2(CH3CN)2]PF6 in water

A facile [Ru(acac)₂(CH₃CN)₂]PF₆ (Hacac = acetylacetone) (1) catalyzed oxidation of alcohols to aldehydes or ketones using H₅IO₆ as oxidant in water at room temperature is described.     

Nucleophilic addition of water to 1-isoquinolinyl phenyl ketone. The synthesis, spectroscopic investigation, crystal and molecular structure and DFT calculations of [ReOBr2(iquinpk-OH)(PPh3)]

The reaction of [ReOBr₃(PPh₃)₂] with 1-isoquinolinyl phenyl ketone in acetone has been examined and the novel complex [ReOBr₂(iquinpk-OH)(PPh₃)] has been obtained. The complex has been characterised by IR, UV–Vis spectroscopy and X-ray crystallography. The electronic structure of [ReOBr₂(iquinpk-OH)(PPh₃)] has been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of [ReOBr₂(iquinpk-OH)(PPh₃)] have been calculated with the time-dependent DFT method and the UV–Vis spectrum has been discussed on this basis.     

Synthesis and crystal structure of carbonate cancrinite Na8[AlSiO4]6CO3(H2O)3.4, grown under low-temperature hydrothermal conditions

The synthesis of cancrinite in the system Na₂O–SiO₂–Al₂O₃–Na₂CO₃–H₂O was studied under low-temperature hydrothermal conditions in the 353 K<T<473 K interval. The aim was to reveal the suitable range for the crystallization of pure-phase carbonate cancrinite with the ideal composition Na₈[AlSiO₄]₆CO₃(H₂O)₂ without cocrystallization of sodalite or intermediate disordered phases between cancrinite and sodalite. It was found that cancrinite formation reacts very sensitive on the temperature within the autoclaves whereas the concentration of reactants and the alkalinity of the hydrothermal solution have a much lower influence on the phase formation. Thus the temperature of crystallization of carbonate cancrinite without any by-products should not remain below 473 K. At the lower reaction temperature of 353 K the formation of a disordered intermediate phase between the cancrinite and the sodalite structure has been obtained in every case, independent of the template concentrations and the base. Some problems to detect this in a typical powder product mixture are discussed. Besides the ²⁹Si and ²⁷Al MAS NMR characterization of the products, the crystal structure refinement of pure carbonate cancrinite of ideal composition Na₈[AlSiO₄]₆CO₃(H₂O)_3.4, has been carried out from X-ray powder data using the Rietveld method: P6₃, a=1271.3(1) pm, c=518.6(1) pm, R_WP=0.073, R_F=0.016 for 347 structure factors and 45 variable positional parameters.     

Direct synthesis and characterization of novel homo- and heterometallic mixed-ligand tetrazolate complexes, Cu(en)(tz)2 and Cu(en)2Zn(tz)4 [en = ethylenediamine, tz = tetrazolate]

For the first time, tetrazolate complexes have been prepared by direct synthesis. Two novel homo- and heterometallic mixed-ligand complexes, Cu(en)(tz)₂ and Cu(en)₂Zn(tz)₄, have been synthesized using tetrazole (Htz), ethylenediamine (en), metallic copper and zinc oxide as starting materials. Both tetrazolates were characterized by single-crystal X-ray diffraction, IR spectroscopy and thermal analysis. The complexes present 1D coordination polymers, with tetrazolate anions acting as both monodentate and bridging ligands.