One-dimensional CaWO4 and CaWO4:Tb3+ nanowires and nanotubes: electrospinning preparation and luminescent properties

One-dimensional CaWO4 and CaWO4:Tb3+ nanowires and nanotubes have been prepared by a combination method of sol-gel process and electrospinning. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL), low voltage cathodoluminescence (CL) and time-resolved emission spectra, as well as kinetic decays were used to characterize the resulting samples. The results of XRD, FT-IR, TG-DTA indicate that the CaWO4 and CaWO4: Tb3+ samples begin to crystallize at 500 degrees C with the scheelite structure. Under ultraviolet excitation and low-voltage electron beams excitation, the CaWO4 samples exhibit a blue emission band with a maximum at 416 nm originating from the WO42- groups, while the CaWO4:Tb3+ samples show the characteristic emission of Tb3+ corresponding to (D4-F6,5,4,3)-D-5-F-7 transitions due to an efficient energy transfer from WO42- to Tb3+.

Rare Earth Fluorides Nanowires/Nanorods Derived from Hydroxides: Hydrothermal Synthesis and Luminescence Properties

In this paper, we reported the synthesis of nearly monodisperse and well-defined one-dimensional (1D) rare earth fluoride(beta-NaREF4) (RE = Y, Sm, Eu, Gd, Tb, Dy, and Ho) nanowires/nanorods by in situ acid corrosion and anion exchange approach using RE(OH)(3) as precursors via a facile hydrothermal route. X-ray diffraction (XRD), energy-dispersive X-ray (EDX) spectroscopy. scanning electron microscopy (SEM), transmission electron microscopy (TEM). high-resolution transmission electron microscopy (HRTEM), and photoluminescence(PL)spectroscopy were used to characterize the samples. The results show that the as-prepared rare earth fluoride (beta-NaREF4) nanowires/nanorods preserve the basic morphology of the initial RE(OH)(3) precursors.

Spindle-like Lanthanide Orthovanadate Nanoparticles: Facile Synthesis by Ultrasonic Irradiation, Characterization, and Luminescent Properties

A general and facile ultrasonic irradiation method has been established for the synthesis of the lanthanide orthovanadate LnVO(4) (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) nanoparticles from an aqueous solution of Ln(NO3)(3) and NH4VO3 without any surfactant or template. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and photoluminescence (PL) spectra as well as kinetic decays were employed to characterize the as-prepared products. Ultrasonic irradiation has a strong effect on the morphology of the LnVO(4) nanoparticles. The SEM and TEEM images illustrate that the as-formed LnVO(4) particles have a spindle-like shape with an equatorial diameter of 30-70 nm and a length of 100-200 am, which are the aggregates of even.

Facile Hydrothermal Synthesis and Luminescent Properties of Large-Scale GdVO4:Eu3+ Nanowires

Large-scale GdVO4:Eu3+ nanowires with diameters of about 15 nm and lengths of several micrometers were achieved by a facile hydrothermal method in the presence of disodium ethylenediamine tetraacetate (Na2H2L). The influences of several parameters, such as pH value, reaction temperature, and molar ratio of Na2H2L to Gd3+ on the final products were investigated. The formation mechanism of the as-obtained GdVO4:Eu3+ nanowires is proposed on the basis of time-dependent experiments. It is found that the organic additive Na2H2L, which acts as a shape modifier, has a dynamic effect by adjusting the growth rates of different facets, resulting in the formation of the GdVO4:Eu3+ nanowires. The luminescent spectrum of GdVO4:Eu3+ nanowires shows the strong characteristic dominant emission of the Eu3+ ions at 614 nm.

Facile chemical conversion synthesis and luminescence properties of uniform Ln3+ (Ln = Eu, Tb)-doped NaLuF4 nanowires and LuBO3 microdisks

Uniform NaLuF(4) nanowires and LuBO(3) microdisks have been successfully prepared by a designed chemical conversion method. The lutetium precursor nanowires were first prepared through a simple hydrothermal process. Subsequently, uniform NaLuF(4) nanowires and LuBO(3) microdisks were synthesized at the expense of the precursor by a hydrothermal conversion process. The whole process was carried out in aqueous condition without any organic solvents, surfactant, or catalyst. The conversion processes from precursor to the final products have been investigated in detail. The as-obtained Eu(3+) and Tb(3+)-doped LuBO(3) microdisks and NaLuF(4) nanowires show strong characteristic red and green emissions under ultraviolet excitation or low-voltage electron beam excitation. Moreover, the luminescence colors of the Eu(3+) and Tb(3+) codoped LuBO(3) samples can be tuned from red, orange, yellow, and green-yellow to green by simply adjusting the relative doping concentrations of the activator ions under a single wavelength excitation, which might find potential applications in the fields such as light display systems and optoelectronic devices.

Coordination-Induced Formation of One-Dimensional Nanostructures of Europium Benzene-1,3,5-tricarboxylate and Its Solid-State Thermal Transformation

Novel one-dimensional europium benzene-1,3,5-tricarboxylate compressed nanorods have been synthesized oil it large scale through direct precipitation in solution phase under moderate conditions without the assistance of any surfactant, catalyst, or template. The obtained nanorods have widths of about 50-100 not, thicknesses of 10-20 nm, and lengths ranging from a few hundred nanometers to several micrometers. X-ray powder diffraction. elemental analysis, Fourier transform infrared Studies, and thermogravimetric and differential thermal analysis show that the nanorods have the structural formula of Eu(1,3,5-BTC)center dot 6H(2)O. Upon UV excitation, these nanorods exhibit a highly efficient luminescence. which comes from the Eu3+ ions. Moreover, Eu2O3 nanorods Could also be obtained via a thermal decomposition method using the corresponding complex as a precursor. This synthetic route is promising for the preparation of other one-dimensional crystalline nanomaterials because of its simplicity and the low cost of the starting reagents.

Four New Lanthanide-Nitronyl Nitroxide (Ln(III)=Pr-III, Sm-III, Eu-III, Tm-III) Complexes and a Tb-III Complex Exhibiting Single-Molecule Magnet Behavior

Five new complexes based on rare-earth-radical [Ln(hfac)(3)(NIT-5-Br-3py)](2) (Ln=Pr (1), Sm (2), Eu (3), Tb (4), Tm (5); hfac = hexafluoroacetylacetonate; NIT-5-Br-3py = 2-(4,4,5,5-tetramethyl-3-oxylimidazoline-1-oxide)-5-bromo-3-pyridine) have been synthesized and characterized by X-ray crystal diffraction. The single-crystal structures show that these complexes have similar structures, in which a NIT-5-Br-3py molecule acts as a bridging ligand linking two Ln(III) ions through the oxygen atom of the N-O group and nitrogen atom from the pyridine ring to form a four-spin system. Both static and dynamic magnetic properties were measured for complex 4, which exhibits single-molecule magnetism behavior.

Remarkable changes in the optical properties of CeO2 nanocrystals induced by lanthanide ions doping

Highly uniform and well-dispersed CeO2 and CeO2:Eu3+ (Sm3+, Tb3+) nanocrystals were prepared by a nonhydrolytic solution route and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), UV/vis absorption, and photoluminescence (PL) spectra, respectively. The result of XRD indicates that the CeO2 nanocrystals are well crystallized with a cubic structure. The TEM images illustrate that the average size of CeO2 nanocrystals is about 3.5 nm in diameter. The absorption spectrum of CeO2:Eu3+ nanocrystals exhibits red-shifting with respect to that of the undoped CeO2 nanocrystals. Under the excitation of 440 nm (or 426 nm) light, the colloidal solution of the undoped CeO2 nanocrystals shows a very weak emission band with a maximum at 501 nm, which is remarkably enhanced by doping additional lanthanide ions (Eu3+, Tb3+, Sm3+) in the CeO2 nanocrystals. The emission band is not due to the characteristic emission of the lanthanide ions but might arise from the oxygen vacancy which is introduced in the fluorite lattice of the CeO2 nanocrystals to compensate the effective negative charge associated with the trivalent ions.

Bifunctional magnetic-optical nanocomposites: Grafting lanthanide complex onto core-shell magnetic silica nanoarchitecture

Anew class of bifunctional architecture combining the useful functions of superparamagnetism and terbium complex luminescence into one material has been prepared via two main steps by a modified Stober method and the layer-by-layer (LbL) assembly technique. The obtained bifunctional nanocomposites exhibit superparamagnetic behavior, high fluorescence intensity, and color purity. The architecture has been characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), UV-vis absorption and emission spectroscopy, X-ray diffraction, and superconducting quantum interference device (SQUID) magnetometry.

Near-infrared luminescent mesoporous materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III), Pr(III)] complexes

New near-infrared-luminescent mesoporous materials were prepared by linking ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complexes to the ordered mesoporous MCM-41 through a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline. The resulting materials (denoted as Ln(hfth)(3)phen-M41 and Pr(tfnb)(3)phen-M41; Ln=Er, Yb, Nd, Sm; hfth = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb = 4,4,4-trifluoro-1-(2-naphthyl)- 1, 3-butanedionate) were characterized by powder X-ray diffraction, N-2 adsorption/desorption, and elemental analysis. Luminescence spectra of these lanthanide-complex functionalized materials were recorded, and the luminescence decay times were measured. Upon excitation at the absorption of the organic ligands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) ions by sensitization from the organic ligands moiety. The good luminescent performances enable these NIR-luminescent mesoporous materials to have possible applications in optical amplification (operating at 1300 or 1500 nm), laser systems, or medical diagnostics.

Assembly of one-dimensional organic luminescent nanowires based on quinacridone derivatives

The quinacridone derivatives N,N'-dialkyl-1,3,8,10-tetramethylquinacridone (CnTMQA, n = 6, 10, 14) were used as building blocks to assemble luminescent nano- and microscale wires. It was demonstrated that CnTMQA with different lengths of alkyl chains display obviously different wire formation properties. C10TMQA and C14TMQA showed a stronger tendency to form 1-D nano- and microstructures compared with C6TMQA. The C10TMQA molecules could be employed to fabricate the wires with different diameters, which exhibited a size-dependent luminescence property. The emission spectrum of the C10TMQA wires with diameters of 200-500 nm shows a broad emission band at 560 nm and a shoulder at around 535 nm, while the emission spectrum of the C10TMQA wires with diameters of 2-3 mu m reveals a narrower emission band at 563 nm. For the CnTMQA-based samples with different morphologies, the emission property change tendency agrees with that of the powder X-ray diffraction patterns of these samples.

Achiral lanthanide alkyl complexes bearing N,O multidentate ligands. Synthesis and catalysis of highly heteroselective ring-opening polymerization of rac-lactide

Alkane elimination reactions of amino-amino-bis(phenols) H2L1-4, Salan H2L5, and methoxy-beta-diimines HL6,7 with lanthanide tris(alkyl) s, Ln(CH2SiMe3)(3)(THF)(2) (Ln = Y, Lu), respectively, afforded a series of lanthanide alkyl complexes 1-8 with the release of tetramethylsilane. Complexes 1-6 are THF-solvated mono( alkyl) s stabilized by O, N, N, O-tetradentate ligands. Complexes 1-3 and 5 adopt twisted octahedral geometry, whereas 4 contains a tetragonal bipyramidal core. Bearing a monoanionic moiety L-6 (L-7), complex 7 ( 8) is a THF-free bis(alkyl). In complex 7, the O, N, N-tridentate ligand combined with two alkyl species forms a tetrahedral coordination core. Complexes 1, 2, and 3 displayed modest activity but high stereoselectivity for the polymerization of rac-lactide to give heterotactic polylactide with the racemic enchainment of monomer units P-r ranging from 0.95 to 0.99, the highest value reached to date. Complex 5 exhibited almost the same level of activity albeit with relatively low selectivity. In contrast, dramatic decreases in activity and stereoselectivity were found for complex 4. The Salan yttrium alkyl complex 6 was active but nonselective. Bis(alkyl) complexes 7 and 8 were more active than 1-3 toward polymerization of rac-LA, however, to afford atactic polylactides due to di-active sites. The ligand framework, especially the "bridge" between the two nitrogen atoms, played a significant role in governing the selectivity of the corresponding complexes via changing the geometry of the metal center.

Pyrrolide-supported lanthanide alkyl complexes. Influence of ligands on molecular structure and catalytic activity toward isoprene polymerization

The N,N- bidentate ligands 2- {( N- 2,6- R) iminomethyl)} pyrrole ( HL1, R) dimethylphenyl; HL2, R) diisopropylphenyl) have been prepared. HL1 reacted readily with 1 equiv of lanthanide tris( alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), affording lanthanide bis(alkyl) complexes L(1)Ln(CH2SiMe3)(2)(THF)(n) (1a, Ln= Lu, n = 2; 1b, Ln = Sc, n = 1) via alkane elimination. Reaction of the bulky ligand HL2 with 1 equiv of Ln(CH2SiMe3)(3)( THF)(2) gave the bis(pyrrolylaldiminato) lanthanide mono(alkyl) complexes L(2)(2)Ln- (CH2SiMe3)(THF) (2a, Ln) Lu; 2b, Ln = Sc), selectively. The N,N- bidentate ligand HL3, 2- dimethylaminomethylpyrrole, reacted with Ln( CH2SiMe3) 3( THF) 2, generating bimetallic bis( alkyl) complexes of central symmetry ( 3a, Ln = Y; 3b, Ln = Lu; 3c, Ln = Sc). Treatment of the N,N,N,N- tetradentate ligand H2L4, 2,2'-bis(2,2-dimethylpropyldiimino) methylpyrrole, with equimolar Lu(CH2SiMe3)(3)(THF)(2) afforded a C-2- symmetric binuclear complex ( 4). Complexes 3a, 3b, 3c, and 4 represent rare examples of THF- free binuclear lanthanide bis( alkyl) complexes supported by non- cyclopentadienyl ligands. All complexes have been tested as initiators for the polymerization of isoprene in the presence of AlEt3 and [ Ph3C][B(C6F5)(4)]. Complexes 1a, 1b, and 3a show activity, and 1b is the most active initiator, whereas 2a, 2b, 3b, 3c, and 4 are inert.

Structural diversity of lanthanide-amino acid complexes under near physiological pH conditions and their recognition of single-stranded DNA

We reported here four structures of lanthanide-amino acid complexes obtained under near physiological pH conditions and their individual formula can be described as [Tb-2(DL-Cys)(4)(H2O)(8)]Cl-2 (1), [Eu-4(mu(3)-OH)(4)(L-Asp)(2)(L-HAsp)(3)(H2O)(7)] Cl center dot 11.5H(2)O (2), [Eu-8-(L-HVal) (16)(H2O)(32)]Cl-24 center dot 12.5H(2)O (3), and [Tb-2(DL-HVal)(4)(H2O)(8)]Cl-6 center dot 2H(2)O (4). These complexes showed diverse structures and have shown potential application in DNA detection. We studied the interactions of the complexes with five single-stranded DNA and found different fluorescence enhancement, binding affinity and binding stoichiometry when the complexes are bound to DNA.