Luminescent Europium Research Articles

Warm red light emitting Eu(III) complexes synthesis and analysis including computational methods for photonic applications

Six luminescent europium organic complexes have been synthesized and studied for their luminescent properties. The synthesized complexes were analyzed through elemental analysis, XRD, SEM, EDAX, FT-IR, NMR and thermogravimetry. The complexes exhibit crystalline behavior and possess decent thermal stability. Photoluminescence study on complexes were conducted in both solid and solution states, the results indicate the characteristic red emission. With the addition of ancillary ligands, water molecules are replaced from inner coordination sphere, leading to enhanced luminescence properties. The colorimetric parameters (CIE, CP%, CCT, u′, v′) suggest aptness of these complexes in red light illuminating OLEDs. The J-O parameters were calculated experimentally and theoretically with the help of LUMPAC software. Theoretical and experimental results agree well reflecting the efficacy of the outcomes. As a result of red emission, these complexes could have interesting photonics applications. The biological studies indicate the probable use of these complexes in the medical industry.

Isomorphism of Sr[Li3AlO4] and Sr[Li3GaO4] - Syntheses, Crystal Structure, and Europium(II) Luminescence.

While highly efficient red-emitting inorganic phosphors have been discovered in the substance class of alkaline earth oxo(nitrido)lithoaluminates, new narrow-band green- and yellow-emitting components are being sought to improve the performance of phosphor-converted light-emitting diodes (pc-LEDs). Various solid-state reactions were carried out under protective gas atmosphere in nickel crucibles and sealed tantalum ampules to synthesize Sr[Li3AlO4], Sr[Li3GaO4], and five substitutional derivates of Sr[Li3(Al1-x Ga x )O4] at moderate temperatures. The observation of a linear increase in the unit cell parameters as a function of the increasing gallium mole fraction x in Sr[Li3(Al1-x Ga x )O4] revealed Vegard behavior in the solid-solution series, which was derived from powder X-ray diffraction data. The isomorphic crystallization of the new oxolithogallate Sr[Li3GaO4] and the known oxolithoaluminate Sr[Li3AlO4] in an ordered variant of the U[Cr4C4] aristotype was verified on the basis of powder and single-crystal X-ray diffraction data. Photoluminescence spectroscopy was used to investigate the narrow-band emissions in the substitution series of Eu2+-activated Sr[Li3(Al1-x Ga x )O4] under blue-light excitation. The emission maximum was shifted to higher energies as the gallium mole fraction increased. Peak wavelengths were observed at λem = 572 nm (fwhm equals 47 nm, 1446 cm-1, 0.18 eV) for yellow-emitting Sr[Li3AlO4]:Eu2+ and at λem = 554 nm (fwhm equals 49 nm, 1589 cm-1, 0.20 eV) for green-emitting Sr[Li3GaO4]:Eu2+. Sr[Li3AlO4]:Eu2+ has excellent thermal quenching resistance with a photoluminescence emission intensity of >93% at T = 423 K relative to the room temperature value, making this inorganic phosphor a potential candidate for solid-state lighting applications.

Octocrylene carboxylate as an antenna in a luminescent Europium(III) complex: Experimental and theoretical insights

A new carboxylic acid, 2-cyano-3,3-diphenyl-2-propenoic acid, CLN, a chromophore ligand, was obtained by an alkaline hydrolysis reaction from the octocrylene, a commercial type B ultraviolet (UVB) radiation absorber. The CLN structure was elucidated by single-crystal X-ray diffraction (SCXRD) as being tetragonal with space group P4‾21/c and the presence of a carboxylic acid group was confirmed by mass, infrared (IR), and proton nuclear magnetic resonance (1H NMR) spectroscopy. In this way, coordination compounds were developed between CLN and Ln(III), Ln = being Gadolinium (Gd) and Europium (Eu), with a stoichiometry of 4:13 metal:ligand, confirmed by thermal and elemental analyses, corroborating with the metal cluster predicted by Sparkle/AM1 semi-empirical model. Photoluminescence data indicated that Eu(III) is efficiently sensitized by CLN due to its triplet excited state, determined using the emission spectrum of the Gd(III) mimic complex (T = 25,477 cm−1), being suitable for this purpose. Therefore, the emission spectrum of the Eu(III) complex exhibited a 5D0 → 7FJ transitions characteristic of the lanthanide ion. Furthermore, the Judd-Ofelt intensity parameters, the radiative and non-radiative decay rates, and the intrinsic quantum yield evaluated using the software LUMPAC software were in good agreement with the experimental values.

The Structure and Optical Properties of Luminescent Europium Terephthalate Antenna Metal-Organic Frameworks Doped by Yttrium, Gadolinium, and Lanthanum Ions.

New heterometallic antenna terephthalate MOFs, namely, (EuxM1-x)2bdc3·4H2O (M = Y, La, Gd) (x = 0.001-1), were synthesized by a one-step method from aqueous solutions. The resulting compounds are isomorphic to each other; the crystalline phase corresponds to Ln2bdc3∙4H2O. Upon 300 nm excitation to the singlet excited state of terephthalate ions, all compounds exhibit a bright red emission corresponding to the of 5D0-7FJ (J = 0-4) f-f transitions of Eu3+ ions. The Eu(III) concentration dependence of the photophysical properties was carefully studied. We revealed that Gd-doping results in photoluminescence enhancement due to the heavy atom effect. To quantitatively compare the antenna effect among different compounds, we proposed the new approach, where the quantum yield of the 5D0 formation is used to characterize the efficiency of energy transfer from the ligand antenna to the Eu3+ emitter.

Circularly polarised luminescence of cholesteric polymer composite with high concentration of europium complex

ABSTRACT A novel method has been developed for fabricating cholesteric liquid crystal polymer composite containing a luminescent europium complex. It involves creating porous cholesteric polymer networks, introducing the europium complex into the pores and encapsulating it through the UV-induced polymerisation of a nematic diacrylate. The resulting composite exhibits bright red luminescence upon excitation by UV light which is strongly circularly polarised. Such materials have potential applications in display technologies, counterfeit protection and other fields.

Sensitive electrochemiluminescence immunosensor based on a novel luminescent europium metal–organic framework and antenna effect for detecting pro-gastrin-releasing peptide

Sensitive detection of pro-gastrin-releasing peptide (Pro-GRP) is crucial because it is a highly sensitive and specific tumor marker for small cell lung cancer. Herein, we synthesized an efficient luminescent europium metal–organic framework and developed a sandwich ECL immunosensor for the sensitive detection of Pro-GRP, which used Eu3+ as the central ion and 2,4,6-tri (4-carboxyphenyl)-1,3,5-triazine (H3TATB) as the organic ligand. H3TATB acted as a strong absorbing reagent and transferred its energy to Eu3+ via the antenna effect to enhance the ECL response signal of Eu3+. As per calculations, the ECL efficiency of Eu-TATB, which was a promising ECL luminophore, was up to 130 %. The Cu2O cube worked as a substrate to assist the electron transfer and was used as a co-reaction accelerator to catalyze S2O82− to produce more SO4•− and then enhance the ECL intensity of Eu-TATB. Under optimal experimental conditions, the ECL immunosensor had a linear range of 5 fg mL−1–50 ng mL−1 for detecting Pro-GRP with a detection limit of 1.6 fg mL−1; moreover, it demonstrated excellent stability and specificity and has been successfully applied for detecting Pro-GRP in the human serum.

Composition-dependent photoluminescence in nanocrystalline La2Hf2-xZrxO7:Eu phosphor: role of chemical twin Zr/Hf environments around a luminescent center.

Based on chemical intuition, linear trends are anticipated in Eu3+ photoluminescence performance inside a pyrochlore matrix of the chemical twins, Hf and Zr, owing to probable geometrical and chemical similarity around the luminescent center. The present work reports the drastically fluctuating result of doping Eu3+ in nanocrystalline pyrochlore, La2Hf2-xZrxO7 (LHZO), matrix on composition variation; the variation is counter to the anticipation-based chemical brotherhood of Hf and Zr. Zirconium-enriched samples of LHZO improve asymmetry around Eu3+ ion leading to enhanced photoluminescence quantum yield (PLQY). The samples with compositions 0.7Hf and 1.3Zr depict the lowest non-radiative channels with the highest theoretically calculated PLQY of ∼71% and excellent thermal stability (∼91%). Synergistic experimental and theoretical analysis reveals that Eu does not unbiasedly occupy La-sites in the pyrochlore LHZO matrix towards chemical twins of Hf and Zr; rather, it energetically prefers to occupy Zr-rich vicinal sites. When the composition with Zr is in the low-medium range, Eu has a higher probability of occupying Zr-rich vicinal sites depicting higher lifetime and PLQY. When Zr-content goes beyond 70-80%, the other site occupancies start contributing leading to a reduction in both lifetime and quantum yield. This work paves a great strategy and provides a futuristic potential to utilize europium luminescence in separating chemically close Hf-Zr for various technological applications.

Luminescent Europium(III) Compounds with Quinaldic Acid

Heteroligand luminescent europium(III) complexes with quinaldic acid and neutral ligands were prepared. The compounds obtained were characterized by elemental analysis, X-ray diffraction, thermal gravimetric analysis, and IR spectroscopy. The composition of the complexes was determined. In the course of thermolysis, the nitrogen-containing ligand molecule is eliminated in one step with exo- and endothermic effects. The compounds are thermally stable up to 260°С. The synthesized coordination compounds were introduced into low-density polyethylene to obtain luminescent polymer materials.

Enhancing c-Si Solar Cell Efficiency in the UV Region: Photophysical Insights into the Use of Eu3+ Complexes for Down-Shifting Layer Applications

[Eu(3DPIQC)3] (where DPIQC = 3-(diphenyl phosphoryl)-1-isoquinolinecarboxylate), a luminescent europium complex with antenna ligands, has been carefully embedded within a polyvinyl butyral (PVB) matrix and the resulting material was used to prepare films used as luminescent down-shifting layers (LDSLs) for crystalline Si-based solar cells. The films were characterized using photoluminescence spectroscopy, atomic force spectroscopy (AFM), UV-Vis spectroscopy, and fluorescence microscopy. The AFM analysis shows films with low surface roughness, while fluorescence microscopy revealed that the Eu complex embedded in PVB assumed a spheroidal configuration, a morphology especially beneficial for optical applications. The so-obtained LDSLs were utilized as energy converters in c-Si solar cells to enhance the utilization of high-energy photons, thereby improving their overall efficiency. The determination of photovoltaic parameters carried out before and after the deposition of the LDSLs on the c-Si cells confirms a positive effect on the efficiency of the cell. The Jsc increases from 121.6 mA/cm2 to 124.9 mA/cm2, and the open circuit voltage (Voc) is found to be unrelated to the complex concentration in the films. The fill factor (FF) remains constant with the Eu concentration. The EQE curves indicate an enhancement in the performance of the photovoltaic cells within the UV region of the spectrum for all coated devices. Electrochemical impedance spectroscopy (EIS) was also carried out in order to analyze the effect of the Eu complex in the charge transfer process of the devices.

Fluorescent and smartphone imaging detection of tetracycline residues based on luminescent europium ion-functionalized the regular octahedral UiO-66-NH2

Antibiotic residues cause extensive damage to food security, thus arousing serious concerns. Hence, rapid and sensitive detection of antibiotic residues is crucial to food safety. This study aimed to propose a portable, visual, intelligent and rapid method for tetracycline detection. We developed a ratiometric fluorescent sensor based on the Eu3+-functionalized regular octahedral UiO-66-NH2 material. The developed sensor could quantify tetracycline in the concentration range of 0.5–200 μM with a detection limit as low as 0.2 μM under the optimum conditions. Furthermore, the analytical results obtained using the designed sensor in the actual samples were basically consistent with those obtained using high-performance liquid chromatography. Based on these achievements, a smartphone application-integrated fluorescent testing paper was designed for facile, intelligent, and visual detection of tetracycline. The integrated portable sensor not only saved cost and time for testing but also provided a forward-looking approach to fast, sensitive detection of antibiotic residues.

Imaging Giant Vesicle Membrane Domains with a Luminescent Europium Tetracycline Complex.

Microdomains in lipid bilayer membranes are routinely imaged using organic fluorophores that preferentially partition into one of the lipid phases, resulting in fluorescence contrast. Here, we show that membrane microdomains in giant unilamellar vesicles (GUVs) can be visualized with europium luminescence using a complex of europium III (Eu3+) and tetracycline (EuTc). EuTc is unlike typical organic lipid probes in that it is a coordination complex with a unique excitation/emission wavelength combination (396/617 nm), a very large Stokes shift (221 nm), and a very narrow emission bandwidth (8 nm). The probe preferentially interacts with liquid disordered domains in GUVs, which results in intensity contrast across the surface of phase-separated GUVs. Interestingly, EuTc also alters GM1 ganglioside partitioning. GM1 typically partitions into liquid ordered domains, but after labeling phase-separated GUVs with EuTc, cholera toxin B-subunit (CTxB), which binds GM1, labels liquid disordered domains. We also demonstrate that EuTc, but not free Eu3+ or Tc, significantly reduces lipid diffusion coefficients. Finally, we show that EuTc can be used to label cellular membranes similar to a traditional membrane probe. EuTc may find utility as a membrane imaging probe where its large Stokes shift and sharp emission band would enable multicolor imaging.

Highly Luminescent Europium(III) Complexes in Solution and PMMA-Doped Films for Bright Red Electroluminescent Devices.

This paper reports the synthesis, structure, photophysical, and optoelectronic properties of five eight-coordinate Europium(III) ternary complexes, namely, [Eu(hth)3(L)2], bearing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione (hth) as a sensitizer and L = H2O (1), dpso (diphenyl sulphoxide, 2), dpsoCH3 (4,4'-dimethyl diphenyl sulfoxide, 3), dpsoCl (bis(4-chlorophenyl)sulphoxide, 4), and tppo (triphenylphosphine oxide, 5) as co-ligands. The NMR and the crystal structure analysis confirmed the eight-coordinate structures of the complexes in solution and in a solid state. Upon UV-excitation on the absorption band of the β-diketonate ligand hth, all complexes showed the characteristic bright red luminescence of the Europium ion. The tppo derivative (5) displayed the highest quantum yield (up to 66%). As a result, an organic light-emitting device, OLED, was fabricated with a multi-layered structure-ITO/MoO3/mCP/SF3PO:[complex 5] (10%)/TPBi:[complex 5] (10%)/TmPyPB/LiF/Al-using complex 5 as the emitting component.

Luminescence and Light-Resistance Features of Mixed Europium–Gadolinium Complexes in Polymer Films

The effect of gadolinium on the luminescence of europium in mixed complexes with thenoyltrifluoroacetylacetone and 1,10-phenanthroline in poly(methyl methacrylate) and polyethylene films has been studied. The scale of change in light resistance with varying the proportion of gadolinium and the concentration of the complex in the polymer has been estimated. An increase in the relative intensity of luminescence in polyethylene with an increase in the proportion of gadolinium in the complexes has been revealed, themagnitude of which corresponds to a similar effect for complexes in the crystalline state. This effect is absent in poly(methyl methacrylate) films; however, the presence of gadolinium lowers the rate of decrease in luminescence intensity during photolysis.

Temperature-Dependent Circularly Polarized Luminescence of a Cholesteric Copolymer Doped with a Europium Complex

The design of new materials for non-contact temperature sensors is an important task for scientists working in the fields of chemistry, physics, and materials science. In the present paper, a novel cholesteric mixture based on a copolymer doped with a highly luminescent europium complex was prepared and studied. It was found that the spectral position of the selective reflection peak strongly depends on temperature and a shift towards shorter wavelengths is observed upon heating with an amplitude of more than 70 nm, from the red to green spectral range. This shift is associated with the existence and melting of clusters of smectic order, as confirmed by X-ray diffraction investigations. The extreme temperature dependence of the wavelength of selective light reflection provides a high thermosensitivity of the degree of circular polarization of the europium complex emission. The highest values of the dissymmetry factor are observed when the peak of selective light reflection fully overlaps with the emission peak. As a result, the highest sensitivity of 65%/K for luminescent thermometry materials was obtained. In addition, the ability of the prepared mixture to form stable coatings was demonstrated. The obtained experimental results, i.e., the high thermosensitivity of the degree of circular polarization, and the ability to form stable coatings allow us to consider the prepared mixture as a promising material for luminescent thermometry.

Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium Luminescence.

A new strategy for the easy polymerization of anionic [Ln(Qcy)4]- (HQcy-4-(cyclohexanecarbonyl)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one) into two-dimensional layers of [AgLn(Qcy)4]n (Ln = Sm, Eu, Gd, Tb and Dy) is proposed by binding the single molecular anions [Ln(Qcy)4]- to silver cations through the coordination of the pyridinic nitrogen atoms of the pyrazolonate rings. The luminescent properties of [AgLn(Qcy)4]n have been studied in detail, and it was shown that the previously described low photoluminescence quantum yield (PLQY) of [Eu(Qcy)4]- is due to Ligand-To-Metal Charge Transfer (LMCT) quenching, which is effectively suppressed in the heterometallic [AgEu(Qcy)4]n polymer. Sensibilization coefficients for H3O[Eu(Qcy)4], [AgEu(Qcy)4]n, and H3O[Sm(Qcy)4] complexes (n ≈ 1) were estimated via theoretical analysis (also by using Judd-Ofelt theory for Sm3+) and PLQY measurements.

Detection of different chemical moieties in aqueous media by luminescent Europium as sensor

Abstract Detection of different chemical moieties especially trace metals is important for humans as well as water safety. In this review, different detectors synthesized by the combination of different ligands with luminescent europium complexes were discussed for the separation of metals and chemical moieties in aqueous media. These detectors displayed high sensitivity and selectivity. The limit-of-detection values were very low indicating that these detectors are best suitable for the sensing of chemical moieties and trace metals. These detectors’ luminescent changes could be noticed with the naked eye.

Effect of buffers and pH in antenna sensitized Eu(III) luminescence

The photophysics of a europium(III) complex of 1,4,7,10-tetraazacycododecane-1,4,7-triacetic acid-10-(2-methylene)-1-azathioxanthone was investigated in three buffer systems and at three pH values. The buffers—phosphate buffered saline (PBS), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), and universal buffer (UB)—had no effect on the europium luminescence, but a lower overall emission intensity was determined in HEPES. It was found that this was due to quenching of the 1-azathioxanthone first excited singlet state by HEPES. The effect of pH on the photophysics of the complex was found to be minimal, and protonation of the pyridine nitrogen was found to be irrelevant. Even so, pH was shown to change the intensity ratio between 1-azathioxanthone fluorescence and europium luminescence. It was concluded that the full photophysics of a potential molecular probe should be investigated to achieve the best possible results in any application.

Luminescent Europium(III) Compounds with Quinaldic Acid

Luminescent Europium(III) Compounds with Quinaldic Acid

Особенности люминесценции керамики на основе кубического (ZR-=SUB=-0.82-x-=/SUB=-HF-=SUB=-x-=/SUB=-Y-=SUB=-0.17-=/SUB=-Eu-=SUB=-0.01-=/SUB=-)O-=SUB=-1.91-=/SUB=-

The ceramics based on cubic (Zr0.82-xHfxY0.17Eu0.1)O1.91 with different contents of hafnium were studied. In the work, the elemental composition of the samples was obtained, the cathodoluminescence (CL) spectra and decay kinetics of europium luminescence were studied. The researched showed increase in the content of hafnium doesn’t affect the position and number of observed bands in the luminescence spectrum. The electric dipole and magnetic dipole radiative transitions ratio was estimated for all samples. It’s demonstrated that a decrease in the local symmetry of the europium ion associated with an increase in the hafnium content. It’s shown the 5D0-7F1 transition Eu3+ decay time doesn’t depend on the hafnium content, but varies significantly in different regions of the sample, which can be attributed to the influence of grain boundaries.

Layered Gadolinium-Europium-Terbium Hydroxides Sensitised with 4-Sulfobenzoate as All Solid-State Luminescent Thermometers

Ternary layered gadolinium-europium-terbium basic chlorides were synthesised using a facile hydrothermal-microwave technique. A continuous series of solid solutions was obtained in a full range of rare earth concentrations. To sensitise the luminescence of Eu3+ and Tb3+, a 4-sulfobenzoate anion was intercalated in the ternary layered rare earth hydroxides using one of two methods—a high-temperature ion exchange or a single-stage synthesis. The luminescent colour of the materials was governed by the gadolinium content: at low and medium gadolinium concentrations (0–70%), layered Gd-Eu-Tb basic sulfobenzoate exhibited a bright red europium luminescence; at high gadolinium content (70–90%), a bright green terbium luminescence was observed. The colour coordinates of layered Gd-Eu-Tb basic sulfobenzoate luminescence depended on the temperature in the physiological range (20–50 °C). The relative thermal sensitivity of the obtained materials was up to 2.9%·K−1.