Ionic liquid-based "all-in-one" synthesis and photoluminescence properties of lanthanide fluorides

A facile route to the synthesis of LnF(3) nanocrystals has been accomplished in three ionic liquids (ILs) (OmimPF(6), OmimBF(4), and BmimPF(6)). The partial hydrolysis of PF6- and BF4- was utilized to introduce a new fluoride source. Uniform LnF(3) (Ln = La, Ce, Pr, Nd, Sm, Eu, Er), Tb3+-doped CeF3, and Eu3+-doped LaF3 nanocrystals could be obtained in a large scale, and the products were up to 0.15 g per 10 mL solvents. In the "all-in-one" systems, the ILs acted as solvents, reaction agents, and templates.

Hydrothermal synthesis of lanthanide fluorides LnF(3) (Ln = La to Lu) nano-/microcrystals with multiform structures and morphologies

Lanthanide fluoride LnF(3) (Ln = La to Lu) nano-/microcrystals with multiform crystal structures (hexagonal and orthorhombic) and morphologies (separated elongated nanoparticles, aggregated nanoparticles, polyhedral microcrystals) were successfully synthesized by a facile, effective, and environmentally friendly hydrothermal method. X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and photoluminescence spectra were used to characterize the samples. The experimental results indicated that the use of NaBF4 is indispensable for obtaining LnF(3) crystal structures.

Phosphonate-Functionalized Polyfluorene as a Highly Water-Soluble Iron(III) Chemosensor

An anionic, phosphonate-functionalized polyfluorene, i.e., poly(9,9-bis(3'-phosphatepropyl)fluorene-alt-1,4-phenylene) sodium salt (PFPNa), has been synthesized by copolymerization of phosphonic acid-substituted 2,7-dibromofluorene and phenyldiboronic ester via direct Suzuki polycondensation reaction in DMF/water. Polymer PFPNa is highly soluble and emissive in water with a solubility of 60 mg/mL and a photoluminescence quantum yield of 75%. The absorption and fluorescence spectra of PFPNa are strongly dependent on pH value owing to the partial protonation of phosphate groups and the aggregation of the polymer chains.

Ethylene polymerization, and the copolymerizations of ethylene with hexene or norbornene with highly active mono(beta-enaminoketonato) vanadium(III) catalysts

Five novel vanadium(III) complexes [PhN = C(R-2)CHC(R-1)O]VCl2(THF)(2) (4a: R-1 = Ph, R-2 = CF3; 4b: R-1 =t-Bu, R-2 = CF3; 4c: R-1 = CF3, R-2 = CH3; 4d: R-1 = Ph, R-2 = CH3; 4e: R-1 = Ph, R-2 = H) have been synthesized and characterized. On activation with Et2AlCl, all the complexes, in the presence of ethyl trichloroacetate (ETA) as a promoter, are highly active precatalysts for ethylene polymerization, and produce high molecular weight and linear polymers. Catalyst activities more than 16.8 kg PE/mmolv h bar and weight-average molecular weights higher than 173 kg/ mol were observed under mild conditions.

Synthesis, structural characterization, and ethylene polymerization behavior of the vanadium(III) complexes bearing salicylaldiminato ligands

Vanadium(III) complexes bearing salicylaldiminato ligands (2a-k) [RN=CH(Ar0)]VCl2(THF)2 (Ar C61714, R = Ph, 2a; p-CF3Ph, 2b; p-CH3Ph, 2c; 2,6-Me2Ph, 2d; 2,6-iPr2Ph, 2e; cyclohexyl, 2f; Ar = C6H3tBu(2), R = Ph, 2g; 2,6-iPr2Ph, 2h; Ar = C6H2tBU2(2,4), R = Ph, 2i; 2,6-iPr2Ph, 2j; Ar = C6H2Br2, R = Ph, 2k) were prepared from VC13(THF)3 by treating with 1.0 equiv of (RN=CH)ArOH in tetrahydrofuran (THF) in the presence of excess triethylamine (TEA).

Reversed micellar solubilization extraction and separation of thorium(IV) from rare earth(III) by primary amine N1923 in ionic liquid

The extraction behavior of thorium(IV) sulfate by primary amine N1923 in imidazolium-based ionic liquid (IL) namely 1-octyl-3-methylimidazolium hexafluorophosphate ([C(8)mim]PF6) was systematically studied in this paper. Results showed that the extraction behavior was quite different from that using conventional solvent as diluent. A reversed micellar solubilization extraction mechanism was proposed for the extraction of thorium(IV) by N1923/[C(8)mim]PF6 via slope analysis method and polarized optical microscopy (POM)/transmission electron microscopy (TEM) observation. The salt-out agent, Na2SO4, was demonstrated to prompt this extraction mechanism.

Mass transfer kinetics of neodymium(III) extraction by calix[4]arene carboxylic acid using a constant interfacial area cell with laminar flow

BACKGROUND: Thermodynamics and kinetics data are both important to explain the extraction property. In order to develop a novel separation technology superior to current extraction systems, many promising extractants have been developed including calixarene carboxylic acids. The extraction thermodynamics behavior of calix[4]arene carboxylic acids has been reported extensively. In this study, the mass transfer kinetics of neodymium(III) and the interfacial behavior of calix[4]arene carboxylic acid were investigated.

The separation of Cerium(IV) from nitric acid solutions containing Thorium(IV) and Lanthanides(III) using pure [C(8)mim]PF6 as extracting phase

The extraction behavior of Ce(IV) along with Th(IV) and Ln(III) (Ln = Ce, Gd, Yb) nitrate by pure ionic liquid, [C(8)mim]PF6, was investigated. [C(8)mim]PF6 alone showed good extraction ability for Ce(IV), while it was slight for Th(IV) and negligible for Ln(III). The extraction behavior of Ce(IV) by [C(8)mim]PF6 was particularly studied, and the most probable extraction mechanism proposed was the anion exchange mechanism. Moreover, the stripping of Ce(IV) from IL phase was also investigated. The Ce(IV) in IL phase can be quantitatively recovered by water.

Ionic liquid-based "all-in-one" synthesis and photoluminescence properties of lanthanide fluorides

A facile route to the synthesis of LnF(3) nanocrystals has been accomplished in three ionic liquids (ILs) (OmimPF(6), OmimBF(4), and BmimPF(6)). The partial hydrolysis of PF6- and BF4- was utilized to introduce a new fluoride source. Uniform LnF(3) (Ln = La, Ce, Pr, Nd, Sm, Eu, Er), Tb3+-doped CeF3, and Eu3+-doped LaF3 nanocrystals could be obtained in a large scale, and the products were up to 0.15 g per 10 mL solvents. In the "all-in-one" systems, the ILs acted as solvents, reaction agents, and templates.

Holmium porphyrin compound liquid crystals: Synthesis and properties

5,10,15,20-Tetra-[(p-alkoxy-m-ethyloxy)phenyl]porphyrin and [5-(p-alkoxy)phenyl-10,15,20-tri-phenyl]porphyrin and their holmium(III) complexes are reported. They display a hexagonal columnar discotic columnar Col(h)) liquid crystal phase and were studied by cyclic voltammetry, surface photovoltage spectroscopy (SPS), electric-field-induced surface photovoltage spectroscopy (EFISPS) and luminescence spectroscopy. Within the accessible potential window, all these compounds exhibit two one-electron reversible redox reactions. Quantum yields of Q band are in the region 0.0045-0.21 at room temperature. The SPS and EFISPS reveal that all the compounds are p-type semiconductors and exhibit photovoltaic response due to pi-pi* electron transitions.

Effect of secondary ligands' size on energy transfer and electroluminescent efficiencies for a series of europium(III) complexes, a density functional theory study

In this paper, a quantum chemistry method was used to investigate the effect of different sizes of substituted phenanthrolines on absorption, energy transfer, and the electroluminescent performance of a series of Eu(TTA)(3)L (L = [1,10] phenanthroline (Phen), Pyrazino[2,3-f][1,10]phenanthroline (PyPhen), 2-methylprrazino[2,3-f][1,10] phenanthroline(MPP), dipyrido[3,2-a:2',3'-c]phenazine(DPPz), 11-methyldipyrido[3,2-a:2',3'c]phenazine(MDPz), 11.12-dimethyldipyrido[3,2-a:2',3'-c]phenazine(DDPz), and benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (BDPz)) complexes. Absorption spectra calculations show that different sizes of secondary ligands have different effects on transition characters, intensities, and absorption peak positions.

Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite

Living characteristics of facilely prepared Ziegler-Natta type catalyst system consisting of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite have been found in the polymerization of 1,3-butadiene in hexane at 40 degrees C. The characteristics have been well demonstrated by: a first-order kinetics with respect to monomer conversion, a narrow molecular weight distribution (M-w/M-n = 1.48-1.52) of polybutadiene in the entire range of polymerization conversion and a good linearity between M-n and the yield of polymer. Feasible post-polymerization of 1,3-butadiene and block co-polymerization of 1,3-butadiene and isoprene further support the living natures of the catalyst bestowed with.

CuIn(WO4)(2) nanospindles and nanorods: controlled synthesis and host for lanthanide near-infrared luminescence properties

CuIn(WO4)(2) porous nanospindles and nanorods were synthesized through a low-cost hydrothermal method without introducing any template or surfactants. An interesting formation mechanism, namely "oriented attachment", was observed for the growth of nanorods based on the experimental process and the anisotropic intrinsic crystalline structure of CuIn(WO4)(2), which is uncommon in such a system. The near-infrared luminescence of lanthanide ions (Er, Nd, Yb and Ho) doped CuIn(WO4)(2) nanostructures, especially in the 1300-1600 nm region, was discussed and of particular interest for telecommunications applications. X-Ray diffraction, scanning electron microscopy, transmission electron microscopy, electron diffraction and photoluminescence spectra were used to characterize these materials.

Construction and Photoluminescence of Monophase Hybrid Materials Derived from a Urea-Based Bis-Silylated Bipyridine

A urea-based bis-silylated bipyridine ligand derived from 4,4'-diamino-2,2'-bipyridine has been prepared. Organic-inorganic hybrid materials with a high loading of lanthanide 2,2-bipyridine moieties were obtained by using the silylated bipyridine as the only siloxane network precursor in the presence of lanthanide ions (or lanthanide complexes). The in-situ formation of lanthanide complexes from lanthanide ions and the silylated bipyridine during the sol-gel processing was confirmed by the luminescence behavior of the obtained hybrid materials and that of the corresponding pure lanthanide complex [Ln(bpy)(2)Cl-3 center dot 2H(2)O].

Injection, Transport, Absorption and Phosphorescence Properties of a Series of Blue-Emitting Ir(III) Emitters in OLEDs: a DFT and Time-Dependent DFT Study

Quantum-chemistry methods were explored to investigate the electronic structures, injection and transport properties, absorption and phosphorescence mechanism of a series of blue-emitting Ir(III) complexes {[(F-2-ppy)(2)Ir(pta -X/pyN4)], where F-2-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = phenyl(1); p-tolyl (2); 2,6-difluororophenyl (3); -CF3 (4), and pyN4 = pyridine-1,2,4-tetrazolate (5)}, which are used as emitters in organic light-emitting diodes (OLEDs). The mobility of hole and electron were studied computationally based on the Marcus theory. Calculations of Ionization potentials (IPs) and electron affinities (EAs) were used to evaluate the injection abilities of holes and electrons into these complexes.