Spectroscopic studies on the luminescence properties of ternary europium complexes with different ligands

In this paper, ligand effect of several bi-dental oxygen (O) and nitrogen (N) ligands on the red luminescence properties of europium ion (Eu³⁺) was studied comprehensively. Absorption, emission, and excitation spectral properties of ternary europium complexes with different combinations of ligands including thenoyl trifluoroacetone (TTA), naphthyl trifluoroacetone (NTA), 2,2′-bipyridyl (bpy) and phenanthroline (Phen) were investigated. Efficient Eu³⁺ red emission was observed with all the combinations of the above mentioned ligands. The most intense emission was found with the all nitrogen coordinated complex Eu(bpy)₂(Phen)₂ while the longest wavelength excitation band was recorded with oxygen-nitrogen mixed NTA-bpy complex Eu(NTA)₁(bpy)₃. With change of the ligands combination and ratio, the Eu³⁺ emission peak changes slightly from 612 to 618 nm. The absorption and excitation spectra of the europium complexes were compared and analyzed referring to the individual absorption spectral properties of the ligands. The relation between ligand-to-metal charge transfer states and luminescence intensities for different complexes was studied.     

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.

     

Excitation energy transfer in europium chelate with doxycycline in the presence of a second ligand in micellar solutions of nonionic surfactants

The complexation of Eu³⁺ with doxycycline (DC) antibiotic in the presence of several second ligands and surfactant micelles of different types is studied by the spectrophotometric and luminescence methods. It is found that the efficiency of excitation energy transfer in Eu³⁺-DC chelate depends on the nature of the second ligand and surfactant micelles. Using thenoyltrifluoroacetone (TTA) as an example, it is shown that the second ligand additionally sensitizes the europium fluorescence, and the possibility of intermediate sensitization of DC and then of europium is shown by the example of 1,10-phenanthroline. In all cases, the excitation energy transfer efficiency was increased due to the so-called antenna effect. The decay kinetics of the sensitized fluorescence of the binary and mixed-ligand chelates in aqueous and micellar solutions of nonionic surfactants is studied and the relative quantum yields and lifetimes of fluorescence are determined.     

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.     

Photosensitized luminescence of thermostable polynuclear Eu(III) complexes

Tetranuclear europium(III) complexes, [Eu₄(μ-O)(L₁)₁₀] (L₁=2-hydroxy-4-octyloxybenzophenone,1) and [Eu₄(μ-O)(L₂)₁₀] (L₂=2-hydroxy-4-dodecyloxybenzophenone,2) were synthesized by the reaction of lanthanide nitrates with L₁ or L₂ in the presence of triethylamine in methanol. The photosensitized emission bands of the both Eu(III) complexes in THF-d₈ were observed around 579, 590, 615, 653, and 699 nm by the excitation of the ligands at 380 nm, whereas the emission from the mononuclear complex 3 containing ethanol molecules was almost quenched. The emission efficiencies were determined to be 3.1±0.1% for 1 and 3.9±0.1% for 2, respectively. The differential scanning calorimetry (DSC) measurements demonstrated that the decomposition points of 1 and 2 were 309 °C and 320 °C, respectively, indicating high thermostability of these complexes compared to the mononuclear Eu(III) complex 3 (250 °C). New strategy for designing stable rare earth compounds giving strong emission would be emphasized by introducing polynuclear complexes. Polynuclear complexes should open a wide range of molecular design for photosensitized luminescence and thermal stability.     

Highly improved electroluminescence from double-layer devices based on a carbazole-functionalized europium<Superscript>3+</Superscript> complex

A novel europium complex Eu(TTA)₃(CPPO)₂ (1) (TTA=thenoyltrifluoroacetone, CPPO=9-[4-(diphenyl-phosphinoyl)-phenyl]-9H-carbazole) based on the phosphine oxide ligand with bipolar structure was used to fabricate double-layer devices. The strong hole injection and transport ability of 1 was proved. The luminance of 414 cd m⁻² was achieved with the device configuration ITO/Eu(TTA)₃(CPPO)₂(40 nm)/BCP (30 nm)/Mg:Ag (BCP = 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline), which is favorable among double-layer organic light emitting devices based on small molecular Eu³⁺ complexes. The maximum current efficiency of 2.44 cd A⁻¹ and external quantum efficiency of 1.55% demonstrate the potential application of 1 as a promising candidate for high-efficiency, simple-structure and pure red-emitting devices.     

Europium doped strontium borate glasses and their optical properties

Optical absorption and luminescence spectra of europium doped strontium borate glasses prepared in different conditions are studied. It is found that the percentage of Eu³⁺ ions varies from 100 to 30% being controlled by the conditions of preparation. The mechanism, favoring reduction of europium to Eu²⁺ state in polycrystalline strontium tetraborate, is much weaker in glasses of the same composition. In samples containing mixed valence europium at densities of 8×10²⁰ cm⁻³, the efficient transfer of optical excitation from Eu³⁺ to Eu²⁺, suppressing the Eu³⁺ luminescence, has been found. The most reliable way of monitoring the percentage of europium ions in different valences for strontium borate glasses is the measuring of absorption at f-f transition ⁷F₀→⁵D₂ of Eu³⁺.     

Design, synthesis and characterization of a highly luminescent Eu-complex monomer featuring thenoyltrifluoroacetone and 5-acryloxyethoxymethyl-8-hydroxyquinoline

A multi-functional ligand, 5-acryloxyethoxymethyl-8-hydroxyquinoline (Hamq), was synthesized, which contained a polymerizable C=C double bond for the copolymerization with other vinyl monomers and acted as photon antenna able to transfer energy to Eu³⁺ ions effectively. The triplet state energy of Hamq was determined to be 22,370 cm⁻¹ via the phosphorescence spectra of Hamq and its gadolinium complex. The title complex monomer Eu(tta)₂(amq) was prepared by coordination reaction of Hamq with europium isopropoxide and 2-thenoyltrifluoroacetone (Htta) in dry organic solvents under argon atmosphere and characterized by elemental analysis and IR spectrum. The photophysical properties of the complex were studied in detail with UV-vis, luminescence spectra, luminescence lifetime and quantum yield. The complex exhibited nearly monochromatic red emission at 612 nm, a remarkable luminescence quantum yield at room temperature (30.6%) upon ligand excitation and a long ⁵D₀ lifetime (389 μs), which indicated that the ligand Hamq could sensitize the luminescence of Eu(III) ion efficiently in Eu(tta)₂(amq), resulting in a strong luminescence of its copolymer poly[MMA-co-Eu(TTA)₂(amq)] under UV excitation. The excellent luminescence properties of the complex made it not only a promising light-conversion molecular device but also an excellent luminescent monomer.     

Preparation and luminescence properties of hybrid materials containing lanthanide complexes covalently bonded to a terpyridine-functionalized silica matrix

New kinds of organic-inorganic hybrid materials consisting of lanthanide (Er³⁺, Eu³⁺, and Tb³⁺) complexes covalently bonded to a silica-based network have been obtained by a sol-gel approach. A new versatile compound containing terpyridine has been synthesized by 4′-p-aminophenyl-2,2′:6′,2″-terpyridine and 3-(triethoxysilyl)propyl isocyanate, which is used as the a ligand of lanthanide ions and also the siloxane network precursor. The obtained hybrid materials were characterized by FT-IR, TGA, DSC, near-infrared, and visible spectrofluorometer, as well as decay analysis. For the Hybrid-Er and Hybrid-Eu, excitation at the ligand absorption wavelength resulted in the typical near-IR luminescence (centered at around 1.54 μm) resulting from the ⁴I_13/2-⁴I_15/2 transition of Er³⁺ ions and strong visible region emission of the Eu³⁺ ions (⁵D₀-⁷F_J), which contributed to the efficient energy transfer from the ligands to the lanthanide ions. However, we have not found strong emission for the Hybrid-Tb. This indicated that the energy transfer did not take place in this system. A model of indirect excitation mechanism to explain the phenomenon was also suggested.     

Rearrangement of optical centers and stimulated radiation of Eu<Superscript>3+</Superscript> in polycrystalline huntite under optical and electron-beam excitation

Polycrystalline europium huntite EuAl₃(BO₃)₄ has been prepared by solid-phase synthesis. The spectral and kinetic characteristics of its luminescence under the excitation by a xenon lamp, single laser pulse, and electron beam have been studied. It has been established that the laser excitation of the polycrystalline samples in the ⁷ F ₀ →⁵ L ₆ transition of Eu³⁺ ions with the power density P ≥ 5 × 10⁷ W/cm² leads to the structure rearrangement of the optical centers, which is accompanied by an increase in the probability of the radiation transitions of the activator. The stimulated radiation of the main type of Eu³⁺ centers in the ⁵ D ₀→⁷ F ₁, ⁷ F ₂, and ⁷ F ₄ transitions has been obtained under the excitation by the electron beam with an energy of 200 keV and a duration of 2 ns.     

Study of lanthanide liquid-crystalline complexes by Photoacoustic and luminescence spectroscopy

Lanthanide complexes Ln(bta)₃L₂ (Ln³⁺: Eu³⁺, Tb³⁺ and Ho³⁺; bta: benzoyltrifluoroacetonate; L: N-octadecyl-2-hydroxy-4-tetradecyloxybenzal- dimine) are synthesized. Their photoacoustic (PA) spectra are reported and interpreted. In the region of ligand absorption, PA intensity increases for Eu(bta)₃L₂, Tb(bta)₃L₂ and Ho(bta)₃L₂, respectively. It is found that the PA intensity of the ligand bears a relation to the intramolecular energy transfer process. By comparison with luminescence spectra, the energy transfer process and phase transition of lanthanide complexes are studied from two aspects: radiative and nonradiative processes.     

Influence of phase and morphology on thermal conductivity of alumina particle/silicone rubber composites

Eu²⁺- and Eu³⁺-Zn₂GeO₄ were prepared by the high temperature solid-state reaction method. The phase purity and crystallinity of Zn₂GeO₄:Eu samples were characterized by X-ray diffraction (XRD). The excitation spectra, the emission spectra and the luminescence decay curves of the Eu²⁺- and Eu³⁺-Zn₂GeO₄ were investigated. Zn₂GeO₄:Eu²⁺ gives a bluish-green luminescence with one emission band located at 467 nm, and Zn₂GeO₄:Eu³⁺ presents an reddish-orange color due to the transition (⁵D₀→⁷F_J, J = 1 and 2) of the Eu³⁺ ions. The luminescence decay curves of Eu²⁺ and Eu³⁺ provide complementary evidence to the mixed valence of europium (Eu²⁺, Eu³⁺) in Zn₂GeO₄ host. These indicate that the mixed valence of europium (Eu²⁺, Eu³⁺) coexists in Zn₂GeO₄ host prepared in an oxidizing atmosphere. The abnormal reduction phenomenon of Eu³⁺→Eu²⁺ in Zn₂GeO₄ host prepared in an oxidizing atmosphere was reported and discussed on the basis of the charge compensation model.     

Photoluminescence of (Ba1−xEux)Si6N8O (0.005≤x≤0.2) phosphors

Eu²⁺-doped BaSi₆N₈O phosphors (Ba_1−xEu_xSi₆N₈O, 0.005≤x≤0.2) were synthesized by gas-pressure sintering of the powder mixture of BaCO₃, Si₃N₄, and Eu₂O₃ at 1750 °C under 0.5 MPa N₂. The fired powder consists of a major BaSi₆N₈O phase and a trace amount of impurity phases. The structural result of the BaSi₆N₈O powder, refined by the Rietveld method, agrees well with that of single crystals. A wide blue luminescence band peaking at about 500 nm is observed in BaSi₆N₈O:Eu²⁺, upon excitation with the ultraviolet light of 310 nm. Although Eu is covalently bonded to six nearest neighbor nitrogen atoms, the luminescence of Eu²⁺ is not significantly redshifted but shows a very narrow excitation spectrum at high energies. The origin of the short-wavelength luminescence is mainly ascribed to a small crystal-field splitting as a result of extremely long distances between europium and nitrogen ligands in BaSi₆N₈O:Eu²⁺.     

Luminescence efficiency of aromatic carboxylates of europium and terbium when methylene bridges and nitro groups are present in the ligands

We discuss the possibility of optimizing the brightness of luminescence for phenylcarboxylates, naphthylcarboxylates, and indolylcarboxylates of europium and terbium and their adducts with 1,10-phenanthroline and 2,2′-bipyridine by modifying the ligands. We have studied the efficiency of luminescence and luminescence excitation. We consider the effect of blocking energy transfer from the ligands to the Eu³⁺ and Tb³⁺ ions by methylene (-CH₂-) bridges dividing the π-electron system of the ligands into two parts and by the electronacceptor nitro group (-NO₂). We have analyzed the pathways for transfer and degradation of the excitation energy at 77 K and 300 K. From the phosphorescence spectra of gadolinium salts, we have determined the energies of the lowest excited triplet states of the ligands. We consider the effect of the relative positions of the triplet levels of the ligands and the excited levels of the Eu³⁺ and Tb³⁺ ions on the luminescence efficiency. We found channels for dissipation of the excitation energy via the ππ* and nπ* states of the aromatic system of the carboxylate and the NO₂ group. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 48–54, January–February, 2007.     

Spectroscopic Characterization of Eu(III) Complexes with New Monophosphorus Acid Derivatives of H<Subscript>4</Subscript>dota

The luminescence lifetimes of europium(III) complexes with new monophosphorus acid derivatives of H₄dota were measured by means of time-resolved laser-induced luminescence spectroscopy in H₂O and D₂O. The hydration numbers of these complexes were estimated using different empirical equations [Horrocks and Sudnick (1979) J. Am. Chem. Soc. 101 (1979) 334; Choppin and Barthelemy(1989) Inorg. Chem. 28, 3354–3357; Choppin and Bünzli Lanthanide probes in life, chemical and earth sciences. Theory and practice (1989); Kimura and Kato J. Alloys Comp. 275–277 (1998) 806; Parker (1999) J. Chem. Soc., Perkin Trans. 2, 493–503; Supkowski and Horroks (2002) Inorg. Chim. Acta. 340, 44–48]. It was shown that all the relationships gave similar results with a satisfactory precision. The hydration numbers of complexes of H₃do3a and H₄dota agreed with the literature values. One water molecule is coordinated in complexes of the new ligands. The results showed that the Choppin formula based on measurements only in H₂O can be satisfactorily used for estimation of the hydration numbers.     

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.     

苯甲酸-镝-钇配合物的发光

合成了苯甲酸-镝-钇固体配合物并研究了它们的光致发光性质.实验结果表明,当苯甲酸镝中部分Dy3+离子被Y3+离子取代时,可以便配合物中Dy3+离子的发光增强.     

Luminescent Properties of a Polymer Photoluminescent Composite Containing the Binuclear (EU,TB) Complex as an Emitter

Uninuclear europium (Eu), as well as binuclear Eu and terbium (Tb), complexes were synthesized using acrylic acid (AA) as the first ligand and 1,10-phenanthroline (Phen) as the second ligand. The relative weight ratio of the europium (III) (Eu³⁺) to terbium (III) (Tb³⁺) ions of the binuclear complex was 1:1 as determined via energy dispersive X-ray analysis. The structures of the Eu(AA)₃Phen and Eu_0.5Tb_0.5(AA)₃Phen complexes were characterized by Fourier transform infrared spectroscopy. A series of tri-cellulose acetate (TCA)/ the Eu(AA)₃Phen and TCA/Eu_0.5Tb_0.5(AA)₃Phen composites were prepared by solution blending, and their luminescent properties were investigated by fluorescence spectrophotometry. The excitation spectra of all composites indicated that the TCA matrix probably affected the energy absorption and transfer of organic ligands. In TCA/Eu_0.5Tb_0.5(AA)₃Phen composites the introduced Tb³⁺ ions had some influence on energy absorption and transfer of organic ligands; the energy transfer process of the complex is suggested to be as follows: Phen→AA→Tb³⁺ion→Eu³⁺ion. The emission spectra indicated that the luminescent intensity of the TCA/Eu_0.5Tb_0.5(AA)₃Phen composites was noticeably stronger than that of the TCA/Eu(AA)₃Phen composites, suggesting that the comparatively stable and high-efficiency energy transfer process was only slightly influenced by the TCA matrix. In summary, the TCA/Eu_0.5Tb_0.5(AA)₃Phen (90/10) composite possesses fine luminescent properties for potential usage as red fluorescent materials.     

A europium(III) organic ternary complex applied in fabrication of?near UV-based white light-emitting diodes

A β-diketone, 2-acetylfluorene-4,4,4-trifluorobutane-1,3-dione (HAFTFBD), and its three europium(III) complexes, Eu(AFTFBD)₃⋅2H₂O, Eu(AFTFBD)₃(TPPO)₂ and Eu(AFTFBD)₃phen, were designed and synthesized, where TPPO was triphenylphosphine oxide and phen was 1,10-phenanthroline. The complexes were characterized by IR, UV-visible, photoluminescence (PL) spectroscopy and thermogravimetric analysis (TGA). The results show that the Eu(III) complexes exhibit a high thermal stability,and wide and strong excitation bands when monitored at 613 nm. Excited by ∼395 nm near UV light, the complexes emitted strong and characteristic red light due to f–f transitions of the central Eu³⁺ ion, and no emission from the ligands was found. The photoluminescence mechanism of the europium(III) complexes was investigated and proposed as a ligand-sensitized luminescence process. Among the three europium(III) complexes, Eu(AFTFBD)₃phen exhibits the highest thermal stability and the most excellent photoluminescence properties. A bright red light-emitting diode was fabricated by coating the Eu(AFTFBD)₃phen complex onto an ∼395 nm-emitting InGaN chip, and the LED showed appropriate CIE chromaticity coordinates (x=0.66, y=0.33). A white LED with CIE chromaticity coordinates (x=0.32, y=0.32) was prepared with Eu(AFTFBD)₃phen as red phosphor, indicating that Eu(AFTFBD)₃phen can be applied as a red component for fabrication of near ultraviolet-based white light-emitting diodes.     

Europium luminescence in fluorite upon high-energy excitation

The reflection and luminescence excitation spectra of CaF₂ crystals containing europium ions in divalent (Eu²⁺) and trivalent (Eu³⁺) states were measured in the range from 4 to 16 eV. It was established that, in CaF₂ : Eu³⁺ crystals, luminescence of Eu³⁺ ions (the f-f transitions) is effectively excited both in the charge-transfer band (at ～8 eV) and in the region of the 4f–5d transitions (at ～10 eV) but is virtually not excited in the fundamental region of the crystal (at an energy higher than 10.5 eV). Luminescence of Eu²⁺ ions (the 427-nm band) in CaF₂ : Eu³⁺ is effectively excited in the fundamental region of the crystal; i.e., luminescence of divalent europium ions occurs through the trapping mechanism. Emission of Eu²⁺ ions in CaF₂ : Eu²⁺ crystals is characterized by the excitation band at an energy of 5.6 eV (the 4f → 5d,t _2g transitions), as well as by the exciton and interband luminescence excitations. The results obtained and data available in the literature are used to construct the energy level diagram with the basic electron transitions in the CaF₂ : Eu crystals.