Self-assembled bright luminescent hierarchical materials from a tripodal benzoate antenna and heptadentate Eu(III) and Tb(III) cyclen complexes

The europium heptadentate coordinatively unsaturated (Eu(III)) and the terbium (Tb(III)) 1,4,7,10-tetraazacyclododecane (cyclen) complexes 1 and 2 were used in conjunction with ligand 3 (1,3,5-benzene-trisethynylbenzoate) to form the supramolecular self-assembly structures 4 and 5;this being investigated in both the solid and the solution state. The resulting self-assemblies gave rise to metal centered emission (both in the solid and solution) upon excitation of 3, confirming its role as a sensitizing antenna. Drop-cased examples of ligand 3, and the solid forms of 4 and 5, formed from both organic and mixture of organic-aqueous solutions, were analyzed using Scanning Electron Microscopy, which showed significant changes in morphology;the ligand giving rise to one dimensional structures, while both 4 and 5 formed amorphous materials that were highly dense solid networks containing nanoporous features. The surface area (216 and 119 m2·g^-1 for 4 and 5 respectively) and the ability of these porous materials to capture and store gases such as N2 investigated at 77 K. The self-assembly formation was also investigated in diluted solution by monitoring the various photophysical properties of 3–5. This demonstrated that the most stable structures were that consisting of a single antennae 3 and three complexes of 1 or 2 (e.g., 4 and 5) in solution. By monitoring the excited state lifetimes of the Eu(III) and Tb(III) ions in H2O and D2O respectively, we showed that their hydration states (the q-value) changed from -2 to 0, upon formation of the assemblies, indicating that the three benzoates of 3 coordinated directly to the each of the three lanthanide centers. Finally we demonstrate that this hierarchically porous materials can be used for the sensing of organic solvents as the emission is highly depended on the solvent environment;the lanthanide emission being quenched in the presence of acetonitrile and THF, but greatly enhanced in the presence of methanol.     

Association of a terpyridine ligand with lanthanide and copper(Ⅱ) nitrates

Reactions between the 1,3-bis(6-methylpyridin-2-yl) pyridine ligand L,C17H15N3 and LnIII(1a,1b,1c,1d) or a mixture of LnIII and CuII nitrates(2a,2b,2c,2d) resulted in a series of respectively novel mono-and heterodinuclea r complexes,where LnIII=Sm(a) ,Eu(b) ,Tb(c) ,Dy(d) . The compounds were char acterized by elemental analysis,ESI-MS and IR spectra,furthermore we obtained crystals of [H2L][Eu(NO3) 5](1b) and [CuL2][Eu(NO3) 5](2b) suitable for XRD char acterization. In the crystal structures the Eu ions are 10-coordinated with quit e a narrow range of Eu-O distances which are between 0.2436 and 0.2556 nm. In 1b the ligand molecule is protonated in both terminal rings,and the N-H groups ar e involved in the N-H…O hydrogen bonds with the same oxygen atom of one of the nitro groups. These hydrogen bonds connect the ions in 1b into the complex which is the principal building block of the structure. In 2b the [CuL2]2+ counterion s are present;the Cu is octahedrally coordinated by all nitrogen iatoms of two L molecules which are therefore almost perpendicular to each other. The electros tatic interactions between the charged species are in both cases the main drivin g force of the crystal packing.     

镧系硬脂酸盐及聚乙烯蜡对HDPE流变性能的影响

利用恒速型、恒压型毛细管流变仪分别考察了镧系硬脂酸盐以及硬脂酸镧与聚乙烯蜡(PE-X)混合物对高密度聚乙烯(HDPE5000S)流变性能的影响。试验结果表明,HDPE加入一定份数的镧系硬脂酸盐以及硬脂酸镧和聚乙烯蜡共混后,熔体的表观黏度降低,产生压力振荡时的滑移长度减少以及信号强度明显减弱。其中以硬脂酸镧及聚乙烯蜡复合体系可以较好地改善聚乙烯的加工流变性。     

Synthesis,spectroscopic characterization,and thermal decomposition kinetics of some lanthanide（Ⅲ） nitrate complexes of 2-（N-o-hydroxyacetophenone） amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene

Complexes of La（Ⅲ）, Ce（Ⅲ）, Pr（Ⅲ）, Nd（Ⅲ）, Sm（Ⅲ）, Eu（Ⅲ）, Gd（Ⅲ）, Dy（Ⅲ）, Yb（Ⅲ）, and Lu0ID with 2-（N-o- hydroxyacetophenone）amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene （HAAT） formed by the condensation of o-hydroxyacetophenone and 2-amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene were synthesized and characterized on the basis of elemental analyses, molar conductance measurements, magnetic susceptibility data, UV-Visible, IR, and NMR spectral studies. The spectral data revealed that the ligand acted as a neutral tridentate coordinating to the metal ion through ONO donor sequence. A coordination number nine was proposed for the complexes. Thermal decomposition studies of the ligand and lanthanum（Ⅲ） complex were carried out and kinetic parameters were calculated using Coats-Redfem equation. The decomposition reactions followed random nucleation mechanism with one nucleus on each particle.     

Pr-CeO2纳米稀土颜料的低温燃烧-水热合成及其表征

以Ce(NO3)3·6H2O,Pr6O11为主要原料,利用低温燃烧-水热合成制备了具有纳米晶粒的Pr-CeO2红色稀土颜料.通过XRD,SEM,EDS,XPS对制备出的Pr-CeO2红色稀土颜料进行了测试分析.结果表明Pr掺杂进入CeO2晶格,形成固溶体,为单一相的萤石型结构.Pr主要是以+3价的形式存在于Pr-CeO2固溶体中,该固溶体中未发现+4价的Pr.水热处理后的颜料粉体晶粒发育更完整,尺寸更均匀,平均尺寸为16.70nm,粉料的呈色性能比水热处理前有明显改善.     

Oxidation Behavior of Lanthanide Aluminum Oxynitrides with Magnetoplumbite-Like Structure

Oxidation in air of lanthanide aluminum oxynitrides LnAl₁₂O₁₈N (Ln=La, Ce, Nd. Pr, Sm, and Gd) of magnetoplumbite-like structure has been studied by X-ray diffraction, infrared transmission, and X-ray photoelectron spectroscopy. Simultaneous recording curves of thermogravimetry and differential thermal analysis have also been performed. These experiments show that oxidation begins at 700° to 800°C, with an increasing rate in the 1000° to 1100°C temperature range. In this process, nitride ions (N^3-) are oxidized. The reaction proceeds up to 1500°C. The oxidation process is accompanied by lattice modifications, which are mainly related to the trapping of neutral atoms (N°) in the structure. The final oxidation products depend on the particular lanthanide element of the pahse. They consist mainly of LnAl₁₁O₁₈, LnAlO₃, and α-Al₂O₃. An interpretation of the oxidation behavior of magnetoplumbite oxynitrides, which are related to the spinel AION oxynitride, is proposed.     

Engineering of Lanthanide‐Doped Upconversion Nanoparticles for Optical Encoding

Lanthanide‐doped upconversion nanoparticles (UCNPs) are an emerging class of luminescent materials that emit UV or visible light under near infra‐red (NIR) excitations, thereby possessing a large anti‐Stokes shift property. Due to their sharp excitation and emission bands, excellent photo‐ and chemical stability, low autofluorescence, and high tissue penetration depth of the NIR light used for excitation, UCNPs have surpassed conventional fluorophores in many bioapplications. A better understanding of the mechanism of upconversion, as well as the development of better approaches to preparing UCNPs, have provided more opportunities to explore their use for optical encoding, which has the potential for applications in multiplex detection and imaging. With the current ability to precisely control the microstructure and properties of UCNPs to produce particles of tunable emission, excitation, luminescence lifetime, and size, various strategies for optical encoding based on UCNPs can now be developed. These optical properties of UCNPs (such as emission and excitation wavelengths, ratiometric intensity, luminescence lifetime, and multicolor patterns), and the strategies employed to engineer these properties for optical encoding of UCNPs through homogeneous ion doping, heterogeneous structure fabrication and microbead encapsulation are reviewed. The challenges and potential solutions faced by UCNP optical encoding are also discussed.     

Solvent Extraction and Separation of Trivalent Lanthanides Using Cyphos IL 104, a Novel Phosphonium Ionic Liquid as Extractant

Solvent extraction of trivalent lanthanides from chloride solution using a novel ionic liquid Cyphos IL 104 (trihexyl(tetradecyl)phosphonium bis-2,4,4-(trimethylpentyl) phosphinate or [R₄PA]) has been investigated, while comparing the results with that of its precursors trihexyl(tetradecyl)phosphonium chloride [R₄PCl or Cyphos IL 101], Cyanex 272 [HA] and their equimolar mixture. The results also indicate very high extractability of Cyphos IL 104 toward trivalent lanthanides. Unlike the conventional acidic extractants, extraction of trivalent lanthanides with Cyphos IL 104 increases the equilibrium pH of the aqueous phase due to the preferential extraction of acid over the lanthanide ions. Extraction mechanism has been established by studying the extraction of neodymium(III) with the ionic liquid as a function of the concentrations of Cyphos IL 104 and chloride ions. Separation studies of trivalent lanthanides from a mixed solution containing 1 × 10^?4M each of La, Nd, Gd, and Lu with Cyphos IL 104 or Cyanex 272 indicate that Cyphos IL 104 is a better extractant in terms of extraction coefficient, but Cyanex 272 exhibits better selectivity toward heavier lanthanides. The prospects of stripping and regeneration of ionic liquid (Cyphos IL 104) have also been discussed in the present study.     

The Influence of the Hofmeister Bias and the Stability and Speciation of Chloridolanthanates on Their Extraction from Chloride Media

The possibility of recovering rare earth elements from solutions containing their chloridometalate anions [LnCl_x]^(x?3)? via the process: LnCl_x^(x?3)? + (x ? 3)L_org + (x–3)H⁺ ? [(LH)_x?3LnCl_x]_org has been tested using 2-(1,3-bis(hexylamino)-1,3-dioxopropan-2-yl)-4,6-di-tert-butylpyridine (PMA), tri-n-butylphosphate (TBP), and tri-n-octylamine (TOA), which are known to be strong extractants for transition metal chloridometalates. While DFT calculations indicate that the formation of the neutral assembly [(PMAH)₃LaCl₆] in the gas phase is favorable, no uptake of La(III) from 6 M HCl by toluene solutions of PMA (or of TBP or TOA) was observed in solvent extraction experiments. Successful uptake of the [PtCl₆]^2? dianion by PMA and the failure to extract the [IrCl₆]^3? trianion under the same conditions indicate that the higher hydration energy of the latter makes transfer to the toluene solution less favorable and that this militates against extraction of La(III) chlorido complexes carrying charges of ?3 or larger in which all the inner-sphere water molecules have been replaced. Computational results confirm literature observations that, in contrast to transition metal trications, formation of REE metalate anions such as [LnCl_x]^(x?3)? is not very favorable, particularly so for chloride, compared with nitrato or sulfato systems. Also, they indicate that the formation of outer-sphere assemblies such as {[La(H₂O)₉]·xCl} in which water ligands are retained in the inner sphere, H-bonded to anions, is more stable than inner-sphere complexes containing an equivalent number of anions. The high level of hydration of such species disfavors their transfer into nonpolar water-immiscible solvents. It is unlikely that recovery of [LnCl_x]^(x?3)? from acidic solutions can be achieved efficiently using currently available anion exchange extractants operating in a “pH-swing” process. Receptors giving very high binding energies to chloridolanthanates will be needed to offset the high dehydration energies required.