Efficient Sensitized Luminescence of Binuclear Ln(III) Complexes Based on a Chelating Bis-Carbacylamidophosphate

Binuclear rare earth complexes Ln₂L₃phen₂ (Ln^III?=?Nd^III, Sm^III, Eu^III, Tb^III, Dy^III, Yb^III and Y^III) with bis-CAPh type ligand - tetramethyl N,N′-(2,2,3,3,4,4-hexafluoro-1,5-dioxopentane-1,5-diyl)bis(phosphoramidate) (H₂L) and 1,10-phenanthroline (phen) were synthesized and characterized by elemental analysis, IR, NMR, absorption and luminescence spectroscopy. Luminescence measurements were performed for all the complexes in solid state and for the Eu^III, Tb^III and Y^III complexes - in solution in DMSO as well. The effective energy transfer from organic ligands to Ln^III ions strongly sensitizes the Ln^III ions emission and under excitation by UV light, the complexes exhibited bright characteristic emission of lanthanide metal centers. It was found that the energy level of the ligands lowest triplet state in the complexes matches better to resonance level of Eu^III rather than Tb^III ion. Depending on temperature the emission decay times of solid europium and terbium complexes were in the range of 1.5–2.0 ms. In solid state at room temperature the Eu^III complex possess intense luminescence with very high intrinsic quantum yield 91% and decay time equal 1.88 ms.

     

Luminescent Behavior of two Novel Thermo-Sensitive Poly(N-isopropylacrylamide) Hydrogels Incorporated with Rare Earth Complexes

Two novel luminescent temperature-sensitive poly(N-isopropylacrylamide) hydrogels fabricated with rare earth (Eu, Tb) picolinic acid complexes were in-situ synthesized within the interpenetration networks. Fluorescence spectra indicate the two functional gels exhibit red for Eu³⁺ species and green emissions for Tb³⁺ ones, respectively, whose luminescence intensities are changed due to temperature increasing from 5 to 30°C until totally quenched at lower critical solution temperature (33°C). In addition, the decreasing luminescence behavior obeys the simple linear equations. The releasing experiment substantiates that there may be complexation between O⩵C–NH⩵ moieties of P-NIPAA and Eu³⁺ ions for the prolonged released time.     

Luminescent Properties of Hybrid Nanostructures Based on Quantum Dots of CdS,Europium 1,3-Diketonate,and Methylene Blue Molecules

The luminescent properties of hybrid nanostructures constructed from colloidal quantum dots (QDs) of CdS passivated with thioglycolic acid, europium(III) tris(tenoyltrifluoroacetonate), and methylene blue dye molecules are studied. Spectral features typical for the formation of core/shell QDs of the CdS/CdS:Eu³⁺ type are found. It is noted that the adsorption of the europium complex at the QD interfaces and the formation of QDs of the CdS/TGA/Eu³⁺ are probable. Spectral patterns that reveal nonradiative energy transfer from the recombination luminescence centers of CdS QDs to the Eu³⁺ ions in the CdS/CdS:Eu³⁺ and CdS/TGA/Eu³⁺ structures are obtained. This is manifested in quenching the recombination luminescence of QDs and in the ignition of the intracentric luminescence of Eu³⁺, which enhance with an increase in the concentration of the europium complex. When such structures are combined with methylene blue molecules, the half-width of the absorption spectra is found to increase by 10–15% with an unchanged position of the absorption band maximum. With an increase in the concentration of methylene blue molecules, decreases in the intensity of the recombination luminescence band of CdS QDs at a wavelength of 530 nm and in the luminescence intensity of Eu³⁺ ions and simultaneously the rise up of the fluorescence of methylene blue at a wavelength of about 675 nm are observed. At the same time, a decrease in the luminescence lifetime of the bands of QDs and europium ions are observed. It is concluded that the nonradiative excitation energy transfer from both the recombination luminescence centers and Eu³⁺ ions to methylene blue molecules takes place.     

Induced assembly and photoluminescence of lanthanum (Tb, Eu, Dy) complexes/ZnO/polyethylene glycol hybrid phosphors

Some novel kinds of hybrid phosphors were assembled with lanthanum (Tb, Eu, Dy) complexes (with four kinds of terbium complexes is 2,4-dihydroxybenzonic acid (DHBA), 1,10-phenanthroline (phen), acetylacetone (AA) and nicotinic acid (Nic), respectively) doped ZnO/PEG particles by co-precipitation approach derived from Zn(CH₃COO)₂ (Zn(AC)₂), NaOH, PEG as precursors at room temperature. The characteristic luminescence spectra for f-f transitions of Tb³⁺, Eu³⁺, Dy³⁺ were observed. It is worthy to point out that ZnO is the excellent host for lanthanum ions by the assembly of PEG matrices.     

Intermolecular energy transfer between lanthanide complexes: 6. Influence of metal-to-ligand ratio on the transfer from terbium (III) to europium (III) complexes of L-histidine

The nature of the complexes formed between Tb³⁺ and L-histidine was investigated by making use of the fact that electronic energy can be absorbed by Tb³⁺/HIS complexes and subsequently transferred in a non-radiative manner to Eu³⁺/HIS complexes. The transfer was found to depend on the possible association of donor and quencher, and this information was used to outline the conditions under which the histidine complexes were found to self-associate. Supplementary information was obtained from measurements of the pH dependence of Tb³⁺ luminescence and differential absorbance spectra of Ho³⁺/HIS complexes. At low pH, the energy transfer occurred primarily by collisional means (implying the presence of monomeric complexes), whereas the transfer was governed by the formation of associated complexes at high pH.     

Intramolecular Energy Transfer and Co-luminescence Effect in Rare Earth Ions (La, Y, Gd and Tb) Doped with Eu3+ β-diketone Complexes

In this paper, Eu³⁺ β-diketone Complexes with the two ligands 1-(2-naphthoyl)-3, 3, 3-trifluoroacetonate (TFNB) and 2’2-bipyridine (bpy) have been synthesized. Furthermore, we reported a systematical study of the co-fluorescence effect of Eu(TFNB)₃bpy doped with inert rare earth ions (La³⁺, Gd³⁺ and Y³⁺) and luminescence ion Tb³⁺. The co-luminescence effect can be found by studying the luminescence spectra of the doped complexes, which means that the existence of the other rare earth ions (La³⁺, Y³⁺, Gd³⁺ and Tb³⁺) can enhance the luminescence intensity of the central Eu³⁺, which may be due to the intramolecular energy transfer between rare earth ions and Eu³⁺. The efficient intramolecular energy transfer in all the complexes mainly occurs between the ligand TFNB and the central Eu³⁺. Full characterization and detail studies of luminescence properties of all these synthesized materials were investigated in relation to co-fluorescence effect between the central Eu³⁺ and other inert ions. Further investigation into the luminescence properties of all the complexes show that the characteristic luminescence of the corresponding Eu³⁺ through the intramolecular energy transfers from the ligand to the central Eu³⁺. Meantime, the differences in luminescence intensity of the ⁵D₀→⁷F₂ transition, in the ⁵D₀ lifetimes and in the ⁵D₀ luminescence quantum efficiency among all the synthesized materials confirm that the doped complex Eu_0.5Tb_0.5(TFNB)₃bpy exhibits higher ⁵D₀ luminescence quantum efficiency and longer lifetime than the pure Eu(TFNB)₃bpy complex and other materials.     

ENHANCED PHOTOLUMINESCENCE OF Eu(III)-ANCHORED POROUS ANODIC ALUMINA FILM

We report here the enhanced luminescence of Eu(III)-anchored porous anodic alumina prepared by self-assembling Eu(III) acetylacetonate, and investigate the luminescence mechanisms. Porous anodic alumina can emit visible light due to a lot of oxygen vacancies formed in the anodic oxidation. The existence of oxygen vacancies resulted in e^?-h⁺ pairs when excited. Eu(II) exists stably by forming Eu²⁺-hole complexes. The enhanced luminescence of Eu(III)-anchored porous anodic alumina is attributed to the complex luminescence of e^?-h⁺ through luminescence center Eu²⁺.     

The co-luminescence effect of a europium (III)-lanthanum (III)-gatifloxacin-sodium dodecylbenzene sulfonate system and its application for the determination of trace amount of europium (III)

A novel co-luminescence system based on the formation of a complex between europium (III) (Eu³⁺) and gatifloxacin (GFLX) in sodium dodecylbenzene sulfonate (SDBS) micelle solution containing lanthanum (III) (La³⁺) has been developed for the determination of Eu³⁺. The experimental results show that the complex formed by Eu³⁺ and GFLX here can emit the characteristic luminescence of Eu³⁺. With the addition of La³⁺, the luminescence intensity of the system was enhanced about 7-fold compared with that without La³⁺. Under the optimal conditions, the luminescence intensity exhibits an excellent linear relationship with Eu³⁺ concentration in the range of 1.0×10⁻¹⁰-5.0×10⁻⁸ mol L⁻¹. The correlation coefficient (r) is 0.9998, and the detection limit (3σ) is 7.0×10⁻¹⁴ mol L⁻¹. A test method with satisfactory accuracy based on this system was applied to determine trace amounts of Eu³⁺ in rare earth samples. In addition, the detailed luminescence mechanism of this system was investigated by analyzing the ultraviolet absorption spectra, surface tension, fluorescence polarization, quantum yield, and the number of water molecules in the first coordination sphere of the Eu³⁺ complex.     

Influence of some selected organic molecules on intensity of luminescence of TiO2:Eu electrodes

Eu³⁺ ions are anchored on TiO₂ matrix by coupling with 2,2′-bipyridyl 4,4′-dicarboxylic acid. Five different luminescence centers are observed for TiO₂|2,2′-bipyridyl 4,4′-dicarboxylic acid|Eu³⁺ electrodes due to electron transitions between d and f orbitals. Photo-luminescence of TiO₂|2,2′-bipyridyl 4,4′-dicarboxylic acid|Eu³⁺ electrodes is increased by attaching 2-thenoyltrifluoroacetone to Eu³⁺ ions. Immersion of TiO₂|2,2′-bipyridyl 4,4′-dicarboxylic acid|Eu³⁺|2-thenoyltrifluoroacetone electrodes in propylsulfide is found to be further increased intensities of luminescence bands by a factor of three.     

Synthesis and luminescent properties of complexes of Eu(III) with 2-thienyltrifluoroacetonate, terephthalic acid and phenanthroline

This work reports the synthesis and luminescent properties of complexes of europium(III) with 2-thienyltrifluoroacetonate (HTTA), terephthalic acid (TPA) and phenanthroline (Phen), in the solid state. The new complexes were characterized by elemental analysis, infrared (IR) spectroscopy, scanning electronic microscopy (SEM) and thermal stability analysis. Both binuclear complex Eu₂(TPA)(TTA)₄Phen₂ and polynuclear complex Eu(TPA)(TTA)Phen present better thermal stability than the mononuclear complex Eu(TTA)₃Phen does. The formation of the binuclear/polynuclear structure of the complexes appears to be responsible for the enhancement of the thermal stability. The emission spectra show narrow emission bands that arise from the ⁵D₀→⁷F_J (J=0-4) transition of the Eu³⁺ ion. The spectral data of the complexes Eu(TPA)(TTA)Phen and Eu₂(TPA)(TTA)₄Phen₂ present only one sharp peak in the region of the ⁵D₀→⁷F₀ transition indicating that only one Eu³⁺ ion species is present in each sample. In addition, the luminescence decay curves of the complexes Eu(TPA)(TTA)Phen and Eu₂(TPA)(TTA)₄Phen₂ fit a single-exponential decay law. The values of quantum efficiencies of the emitting ⁵D₀ level for the complexes Eu(TPA)(TTA)Phen and Eu₂(TPA)(TTA)₄Phen₂ are 29% and 28%, respectively.     

Theoretical and experimental photophysical studies of the tris(4,4,4-trifluoro-1-(1-naphthyl)-1,3-butanedionate) (2,2′-bipiridyl)-europium(III)

The complexes tris(4,4,4-Trifluoro-1-(1-naphthyl)-1,3-butanedionate) (2,2′-bipiridyl) Ln(III), Ln(tan)₃bipy, where Ln(III)=Eu³⁺ and Gd³⁺ have been synthesized, characterized and their photophysical properties (absorption, excitation and luminescence spectra and emission quantum yield) investigated down to 4.2 K. The Eu(tan)₃bipy complex has its molecular structure experimentally determined using X-ray crystallography and theoretically using the SMLC/AM1 method as well as their electronic singlet and triplet states were calculated, using the INDO/S-CI method with a point charge model to represent the Eu³⁺ ion, where two values were adopted, +3.0e and +3.5e, to investigate the imperfect shielding of the 4f shells. The so calculated +3.5e model electronic absorption spectrum and low lying triplet state energies agreed very well with the experimental ones. The emission quantum yield of the Eu³⁺ complex is quite low at room temperature, namely 7%, probably due to the too low lying triplet state, 19,050 cm^-1, and increases by a factor of three when the temperature is lowered to 4.2 K. This strong thermal effect indicates the presence of a channel deactivating the main emitting state, what can be due to a LMCT state possibly lying in the same spectral region, as usually found in Eu³⁺ compounds.     

The photoluminescence,afterglow and up conversion photostimulated luminescence of Eu3+ doped Mg2SnO4 phosphors

The Mg₂SnO₄:Eu³⁺ phosphor with reddish photoluminescence, green afterglow and photostimulated luminescence is obtained by the solid state method. The host related afterglow is greatly enhanced by doping of Eu³⁺ and it can last nearly 6 h when the Eu³⁺ concentration is 1 mol%. The photostimulated luminescence is found to be weakened by doping of Eu³⁺. It was revealed that all the shallow traps and a part of the deep traps are involved in afterglow. The majority of deep traps are responsible for photostimulated luminescence. The impact of doping Eu³⁺ on the afterglow and photostimulated luminescence is investigated and we propose a feasible interpretation.     

The special features of the luminescence and light resistance of europium complexes and their mixtures with lanthanum complexes in polymethyl methacrylate

The kinetics of luminescence and transformation of short-lived products of the photolysis of europium and lanthanum complexes with thenoyltrifluoroacetone and 1,10-phenanthroline and their mixtures in polymethyl methacrylate films was studied by the nanosecond laser photolysis method with recording both light emission and absorption. Fast (535 and 585 nm, ⁵ D ₁ → ⁷ F ₀, ⁷ F ₃, decay time 0.7 μs) and slow (613 nm, ⁵ D ₀ → ⁷ F ₂, luminescence rise and decay times 0.7 μs and 0.5 ms, respectively) luminescence was studied. Induced absorption with a maximum at 600 nm and decay time ∼3 ms was observed; this absorption was assigned to triplet states of the deprotonated form of thenoyltrifluoroacetone. The dependences of luminescence intensity on the concentration of the components in a mixture of complexes were analyzed, and synergistic effects of luminescence strengthening were estimated. The kinetics of a decrease in luminescence intensity during photolysis was studied. Possible mechanisms of a decrease in the relative initial process rate and an increase in the quasi-stationary value of relative luminescence intensity as the concentration of complexes in the polymer increased were discussed.     

Enhanced electroluminescence of Eu by Tb in complexes Tb1−xEux(TTA)3Dipy

A series of rare earth ternary compounds of Tb_1−xEu_x(TTA)₃Dipy (HTTA=thenoyltrifluoroacetone, Dipy=2,2′-dipyridyl) have been synthesized, and the characteristics of the compounds have been performed by DTA-TG, IR, UV and fluorescence spectroscopy. Photoluminescence measurements indicated that the complexes of Eu(III) emit strong red luminescence under UV radiation. IR spectra suggest that complexes have been successfully synthesized, and TG curves indicate that the complexes are stable up to a temperature of about 220 °C. The Eu complex was blended with poly(N-vinylcarbazole) (PVK) and spin coated into films, and electroluminescence devices with the structure of Indium Tin Oxide (ITO)/PVK:Tb_1−xEu_x(TTA)₃Dipy/BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)/aluminum quinoline (AlQ)/Al were fabricated, the luminescence of Eu³⁺ complexes enhances after doping with Tb³⁺. Therefore, it may be an effective method to improve the EL intensity of the lanthanide complex.     

Study on relationship of luminescence in CaS:Eu,Sm and dopants concentration

In order to study different characteristic luminescence of Eu²⁺ and Sm³⁺, delayed photoluminescence (DPL) and infrared stimulated luminescence (ISL) spectra of CaS doped with europium and samarium have been investigated. The influence of Eu and Sm concentration on luminescence of Eu²⁺ in photoluminescence (PL) and ISL was respectively studied. It was found that, at low doping levels, PL emission intensity of Eu²⁺ increased linearly with increment of Eu, while decreased linearly with increment of Sm. However, further increment of Eu and Sm in CaS:Eu,Sm could not increase either the luminescent centres of Eu²⁺ or electron trapping sites of Sm³⁺. Different local environment of Eu²⁺ and Sm³⁺ in the lattice position is thought to be the cause of all observed luminescence phenomena. Finally, the maximum emission in ISL was obtained at 1000 ppm europium and 750 ppm samarium.     

White-light-emitting Eu(III)-bi-doped macromolecular complexes

We have synthesized heterometallic complexes based on a copolymer of acrylic acid with butyl methacrylate (BMAC) with a composition [Eu _x Bi_{(1 ? x)}-BMAC]. These complexes have several emission bands in the visible range. At room temperature, in complexes with a content of Eu(III) of 30–40%, intense white luminescence appears.     

VUV sensitisation of Eu emission by Tb in Ba3Tb(PO4)3-Eu

The luminescence properties of Ba₃Tb_0.9Eu_0.1(PO₄)₃ and Ba₃Gd_0.9Eu_0.1(PO₄)₃ phosphors were studied for excitation over the 120-300 nm wavelength range. It is found that Tb³⁺, which exhibits a strong vacuum-ultraviolet (VUV) absorption band, provides sensitisation of Eu³⁺ emission in this host. This effect can be used to develop phosphors with enhanced conversion efficiency of the VUV radiation into visible light.     

A Mechanism of the influence of Gd(III) and other Ln(III) ions on sensitized luminescence of Eu(III) and Tb(III) ions in aqueous and ethanol solutions: The role of hydroxyl bridges

We studied sensitization of Eu(III) and Tb(III) ions by molecules of 1,10-phenanthroline and 2,2-bipyridil in D₂O and d ₆-ethanol and the influence of Nd(III), Pr(III), Sm(III), Gd(III), and Ho(III) ions on the luminescence intensity I _lum and lifetime τ_lum of Eu(III) and Tb(III) in solutions. The stability constants of complexes of Eu(III) and Gd(III) with 2,2′-bipyridil are measured by spectrophotometric and luminescence methods. It is shown that luminescence of Eu(III) is quenched by Gd(III) ions at the ion concentration equal to 10^?2–10^?1 M, which is caused by competing between these ions for a sensitizer. At the concentration of Ln(III) ions equal to 10^?6?10^?3 M, the sensitized luminescence of Eu(III) and Tb(III) was quenched and τ_lum decreased in the presence of Nd(III) ions, whereas in the presence of Gd(III) the luminescence intensity increased. It is proved that a bridge that connects the two ions upon energy transfer is formed by hydroxyl groups. The intensity of luminescence of Eu(III) and Tb(III) in aqueous solutions and its lifetime decreased in the presence of hydroxyl groups, while upon addition of Gd(III) to these solutions these quantities were restored. We also found that the addition of Gd(III) to deoxygenated ethanol solutions of 2,2′-bipyridil and Eu(III) slows down photochemical and thermal reactions between bipyridil and Eu(III), resulting in the increase in the luminescence intensity of Eu(III).     

Luminescence studies on lanthanide ions (Eu, Dy and Tb) doped YAG:Ce nano-phosphors

Yttrium aluminum garnet nanoparticles both undoped and doped with lanthanide ions (Ce³⁺, Eu³⁺, Dy³⁺ and Tb³⁺) having average size around 30 (±3 nm) nm were prepared by glycine nitrate combustion method followed by annealing at a relatively low temperature of 800 °C. Increase in the annealing temperature has been found to improve the luminescence intensity and for 1200 °C heated samples there exists strong energy transfer from Tb³⁺ to Ce³⁺ ions in YAG:Ce(2%),Tb(2%) nanoparticles as revealed by luminescence studies. Co-doping the YAG:Ce nanoparticles with Eu³⁺ results in significant decrease in the emission intensity of both Ce³⁺ and Eu³⁺ ions and this has been attributed to the oxidation of Ce³⁺ to Ce⁴⁺ and reduction of Eu³⁺ to Eu²⁺ ions. Dy³⁺ co-doping did not have any effect on the Ce³⁺ emission as there is no energy transfer between Dy³⁺ and Ce³⁺ ions.     

Preparation and characterization of nanosized (Y,Bi)VO4:Eu and Y(V,P)O4:Eu red phosphors

Nanosized luminescent (Y,Bi)VO₄:Eu³⁺ and Y(V,P)O₄:Eu³⁺ were synthesized at low temperatures either by a coprecipitation method or by a hydrothermal method from aqueous solutions. The effect of Bi³⁺ ion or P⁵⁺ ion content in the lattice, annealing temperature effects on the crystal structure and the particle size, and the luminescence property of (Y,Bi)VO₄:Eu³⁺ and Y(V,P)O₄:Eu³⁺ nanoparticles were examined with a field-enhanced scanning electron microscopy, XRD, and a spectrofluorometer. The pristine YVO₄:Eu³⁺, (Y,Bi)VO₄:Eu³⁺, or Y(V,P)O₄:Eu³⁺ nanoparticles are 35-50 nm in size. The luminescence spectrum of the Eu³⁺ ion was used to probe its position in the crystal lattice. The dopant ions enter the same lattice sites in the nanocrystalline as in the corresponding bulk material, resulting similar spectral features between them. Photoluminescence intensity is weak for the pristine nanoparticles. Annealing the nanoparticles at temperatures up to 1000 °C results in the increased luminescence intensity (>80% of micrometer-sized phosphors) with the minimal particle growth and the improved particle crystallinity.