Europium Complexes Research Articles

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.

A combined experimental-molecular modeling study of crown ether europium complexes: Effects of the coordinated anion on structural and luminescence properties

It is reported the synthesis, characterization by elemental analysis, thermogravimetry; electronic absorption, infrared, excitation, and emission spectroscopies of the [Eu(12C4)(phen)2(X)n]X2 complexes, where 12C4 = 12-crown-4, phen = 1,10-phenanthroline, and X = F−, Cl−, Br−, SCN−, ClO4−, and NO3−. It is verified that the polarizability of the anion X– exerts remarkable effects on the emission process. As a general trend, lower wavenumbers for the 7F0→5L6, 7F0→5D2 and 7F0→5D1 transitions are associated with the anions with higher volumes and, consequently, higher polarizability. The molecular modeling results performed with quantum methods (RHF and DFT) suggest some relationships between the calculated structures, electronic, and luminescence properties with the presence of the LMCT (ligand-to-metal charge transfer) states, which explains the differences in the emission spectra of these complexes due to the coordinated anion.

Molecular Vibrations in Chiral Europium Complexes Revealed by Near-Infrared Raman Optical Activity.

Raman optical activity (ROA) is commonly measured with green light (532nm) excitation. At this wavelength, however, Raman scattering of europium complexes is masked by circularly polarized luminescence (CPL). This can be avoided using near-infrared (near-IR, 785nm) laser excitation, as demonstrated here by Raman and ROA spectra of three chiral europium complexes derived from camphor. Since luminescence is strongly suppressed, many vibrational bands can be detected. They carry a wealth of structural information about the ligand and the metal core, and can be interpreted based on density functional theory (DFT) simulations of the spectra. For example, jointly with ROA experimental data, the simulations make it possible to determine absolute configuration of chiral lanthanide compounds in solution.

Development of europium(III) complex fluorescent probe for hydrogen sulfide detection and its application in water samples.

Hydrogen sulfide (H2 S) is a crucial endogenous signaling component in organisms that is involved in redox homeostasis and numerous biological processes. Modern medical research has confirmed that hydrogen sulfide plays an important role in the pathogenesis of many diseases. Herein, a fluorescent probe Eu(ttbd)3 abt based on europium(III) complex was designed and synthesized for the detection of H2 S. Eu(ttbd)3 abt exhibited significant quenching for H2 S at long emission wavelength (625 nm), with rapid detection ability (less than 2min), high sensitivity [limit of detection (LOD) = 0.41 μM], and massive Stokes shift (300 nm). Additionally, this probe showed superior selectivity for H2 S despite the presence of other possible interference species such as biothiols. Furthermore, the probe Eu(ttbd)3 abt was successfully applied to detect H2 S in water samples.

Flour moisture detection with an europium-based luminescent probe

In this work, we describe the application of the self-assembled europium complex 1:Eu(III) (where 1: diethyl 8-methoxy-2-oxo-1,2,4,5-tetrahydro-cyclopenta[de]quinolin-3-yl)phosphonate) for the analysis of water content of wheat flour. The methodology herein described represents a robust and accurate way for the detection of small amounts of water in food, providing comparing results with well-established methods such as thermogravimetry and Karl-Fischer titration. Interestingly, as an advantage over other methods, our luminescence-based approach can be implemented in lab-on-a-chip microfluidic devices for real-time and on-line detection of water content of food samples. Additionally, the remarkably long luminescence lifetime of Eu(III) allows the use of state-of-the-art imaging strategies based on PLIM microscopy for the direct visualization of unique water content maps of wheat flour particles.

A Novel ppb-Level Sensitive and Highly Selective Europium-Based Diketone Luminescent Sensor for the Quantitative Detection of Aluminum Ions in Water Samples

A novel Eu(tta)3([4,4′-(t-bu)2-2,2′-bpy)] complex (tta-thenoyltrifluoroacetone), a ratiometric luminescent-based optical sensor for the quantitative determination of aluminum ion, is synthesized and characterized using XRD and 1H NMR. The XRD data reveal the slightly distorted octahedral structure. The complex displays a bright red emission at 613 nm in methanol which is characteristic of europium (III) complexes. Upon the addition of Al3+ ions, the red emission disappears, and a new blue emission at 398 nm emerges, manifesting the ratiometric nature of the complex. The turn-off of the red emission and turn-on of the blue emission are attributed to Eu-Al trans-metalation, as supported by Raman data that show the emergence of Al-O vibrations at 418, 495, and 608 cm−1 concomitant with the disappearance of Eu-O and Eu-N bond vibrations. Most aluminum sensors are known to suffer from interferences from other metals including Cu2+, Co2+, and Cd2+. However, the sensor reported here is tested for 11 common cations and shows no interference on sensitivity. To the best of our knowledge, this is the first known Eu-based luminescence sensor that successfully exhibited the ability to detect aluminum ions in ppb levels in aqueous environments. The calculated Al3+ binding constant is 2.496 × 103 ± 172. The complex shows a linear relationship in the range of 0–47.6 ppb (1.76 × 10−6 M) Al3+ and the limit of detection (LOD) is 4.79 ppb (1.77 × 10−7 M) in MeOH. ICP-OES is used for validation of the sensor complex in water and then it was used for quantitative detection of Al3+ ions in water as a real-life application. The complex can accurately detect Al3+ ions in the range of 4.97–24.9 ppb (1.84 × 10−7 M–9.2 × 10−7 M) with an LOD of 8.11 ppb (2.99 × 10−7 M). Considering that the aluminum ion serves no recognized function within the human body, its accumulation can lead to severe neurological disorders, including Parkinson’s and Alzheimer’s diseases. With the LOD value significantly lower than the WHO-recommended maximum permissible level of 200 ppb for aluminum in drinking water, even without high-power laser-aided signal enhancement, the sensor shows promise for detecting trace amounts of aluminum contamination in water. Therefore, it can significantly aid in the monitoring of even the smallest aluminum ion contamination in drinking water, industrial effluents, and natural water bodies.

Targeted, Molecular Europium(III) Probes Enable Luminescence-Guided Surgery and 1 Photon Post-Surgical Luminescence Microscopy of Solid Tumors.

Discrete luminescent lanthanide complexes represent a potential alternative to organic chromophores due to their tunability of optical properties, insensitivity to photobleaching, and large pseudo-Stokes shifts. Previously, we demonstrated that the lack of depth penetration of UV excitation required to sensitize discrete terbium and europium complexes can be overcome using Cherenkov radiation emitted by clinically employed radioisotopes in situ. Here, we show that the second-generation europium complexes [Eu(III)(pcta-PEPA2)] and [Eu(III)(tacn-pic-PEPA2)] (Φ = 57% and 76%, respectively) lower the limit of detection (LoD) to 1 nmol in the presence of 10 μCi of Cherenkov emitting isotopes, 18F and 68Ga. Bifunctionalization provides access to cysteine-linked peptide conjugates with comparable brightness and LoD. The conjugate, [Eu(tacn-(pic-PSMA)-PEPA2)], displays high binding affinity to prostate-specific membrane antigen (PSMA)-expressing PC-3 prostate cancer cells in vitro and can be visualized in the membrane-bound state using confocal microscopy. Biodistribution studies with the [86Y][Y(III)(tacn-(pic-PSMA)-PEPA2)] analogue in a mouse xenograft model were employed to study pharmacokinetics. Systemic administration of the targeted Cherenkov emitter, [68Ga][Ga(III)(PSMA-617)], followed by intratumoral injection or topical application of 20 or 10 nmol [Eu(III)(tacn-(pic-PSMA)-PEPA2)], respectively, in live mice resulted in statistically significant signal enhancement using conventional small animal imaging (620 nm bandpass filter). Optical imaging informed successful tumor resection. Ex vivo imaging of the fixed tumor tissue with 1 and 2 photon excitation further reveals the accumulation of the administered Eu(III) complex in target tissues. This work represents a significant step toward the application of luminescent lanthanide complexes for optical imaging in a clinical setting.

A wearable gloved sensor based on fluorescent Ag nanoparticles and europium complexes for visualized assessment of tetracycline in food samples.

The abuse of tetracycline antibiotics leads to accumulating residues in the human body, seriously affecting human health. Establishing a sensitive, efficient, and reliable method for qualitative and quantitative detection of tetracycline (TC) is necessary. This study integrated silver nanoclusters and europium-based materials into the same nano-detection system to construct a visual and rapid TC sensor with rich fluorescence color changes. The nanosensor has the advantages of a low detection limit (10.5nM), high detection sensitivity, fast response, and wide linear range (0-30μM), which can meet the analysis requirements of different types of food samples. In addition, portable devices based on paper and gloves were designed. Through the smartphone's chromaticity acquisition and calculation analysis application (APP), the real-time rapid visual intelligent analysis of TC in the sample can be realized, which guides the intelligent application of multicolor fluorescent nanosensors.

Investigating the long-term stability of photoluminescence lifetimes in PMMA films doped with β-diketonate europium complexes based on bipyridine and terpyridine derivatives

In this work, two β-diketonate ligands: dibenzoylmethane (DBM) and Hexafluoroacetone (hfac) have been selected to synthesize a series of β-diketonate europium complexes based on bipyridine and terpyridine derivatives. These complexes were then incorporated into PMMA films to comprehensively investigate their thermal and long-term photoluminescence stability. Comparatively, Eu(hfac)3L1-5 demonstrated higher heat resistance than Eu(DBM)3L1-5, as indicated by their respective initial decomposition temperatures. Various aspects including absorbance, excitation, and emission were examined in solution, powder, and within the PMMA-doped films. Notably, the complexes exhibited a remarkable red emission peak at 613nm and a high photoluminescence quantum yield. To assess their stability, the films were subjected to light, indoor, and dark storage conditions for 720h, with photoluminescence measurements recorded at both 0h and 720h. The results revealed that the hfac-based europium complexes (Eu(hfac)3L1-5) demonstrated good stability under light, indoor, and dark conditions compared to the DBM-based europium complexes (Eu(DBM)3L1-5). This study highlights the direct impact of the β-diketonate ligand structure on the stability of such complexes in films, thus showcasing their potential for future applications in stable optoelectronic devices.

Luminescent Hybrid BPA.DA-NVP@Eu2L3 Materials: In Situ Synthesis, Spectroscopic, Thermal, and Mechanical Characterization.

A series of homogeneous hybrid BPA.DA-NVP@Eu2L3 materials were obtained through an in situ approach where the luminescent dopant was formed at the molecular level with different contents (0.1; 0.2; 0.5; 1; and 2% by weight). A Europium(III) complex (Eu2L3) with quinoline-2,4-dicarboxylic acid was applied as a luminescence additive while a polymer matrix consisted of a combination of bisphenol A diacrylate (BPA.DA) and N-vinylpyrrolidone (NVP) monomers. Synthesis steps and the final materials were monitored by NMR and Fourier transform infrared spectroscopy (FTIR). The emission, excitation spectra, lifetime, and quantum yield measurements were applied for the determination of the photophysical characteristics. The thermal and mechanical properties of the obtained materials were tested via thermal analysis methods (TG/DTG/DSC and TG-FTIR) in air and nitrogen atmospheres, dynamic mechanical analysis (DMA), and hardness and bending measurements. Generally, even a small addition of the metal complex component causes changes in the thermal, mechanical, and luminescent properties. Hybrid materials with a greater europium complex content are characterized by a lower stiffness and hardness while the heterogeneity and the flexibility of the samples increase. A very small amount of an Eu2L3 admixture (0.1% wt.) in a hybrid material causes an emission in the red spectral range and the luminescence intensity was reached for the BPA-DA-NVP@1%Eu2L3 material. These materials may be potentially used in chemical sensing, security systems, and protective coatings against UV.

Impact of stereoisomer multiplicity on the luminescence analysis of europium complexes

The present article explores the challenges arising from the extensive range of plausible stereoisomers found in europium complexes and their implications for the analysis and interpretation of luminescence data. Our main finding reveals that a wide array of plausible stereoisomer geometries, including those generated by the Complex Build Software (which outputs a proven complete set of stereoisomers, given a coordination number and polyhedron shape), can effectively fit photophysical data using regularly employed Judd-Ofelt founded luminescence formalisms. Employing such methodologies always start from a presumed input geometry, usually either solid-state crystallographic geometries, or manually constructed geometries that are later optimized using theoretical model chemistries. But our preliminary analysis of crystallographic databases identified many distinct stereoisomers from several deposited crystallographic input files of europium complexes sharing the same molecular formula. Likewise, the extensive range of theoretically possible stereoisomers available for molecular modeling frequently goes unnoticed. Unaware of this extensive range of both experimental and theoretically possible stereoisomers available, researchers run the risk of inadvertently selecting one that bears no resemblance to reality, potentially overlooking the existence of alternative configurations. Thus, utilizing what ultimately amounts to a randomly selected structure—one that may not faithfully depict the true stereoisomer present in the sample under examination—does not guarantee consistency. Adding intricacy to the matter at hand, the transition from a solid-state environment to a solution can further trigger restructuring phenomena among these stereoisomers. Nevertheless, despite these challenges, our results suggest that luminescence analysis still holds some potential for extracting valuable structural information. For instance, the geometries of cubic shape CU-8, explored for the case studies we present, were the only ones that could not be adjusted, indicating a low likelihood of accurately representing their actual structures.

Low-rate smartphone videoscopy for microsecond luminescence lifetime imaging with machine learning.

Time-resolved techniques have been widely used in time-gated and luminescence lifetime imaging. However, traditional time-resolved systems require expensive lab equipment such as high-speed excitation sources and detectors or complicated mechanical choppers to achieve high repetition rates. Here, we present a cost-effective and miniaturized smartphone lifetime imaging system integrated with a pulsed ultraviolet (UV) light-emitting diode (LED) for 2D luminescence lifetime imaging using a videoscopy-based virtual chopper (V-chopper) mechanism combined with machine learning. The V-chopper method generates a series of time-delayed images between excitation pulses and smartphone gating so that the luminescence lifetime can be measured at each pixel using a relatively low acquisition frame rate (e.g. 30 frames per second [fps]) without the need for excitation synchronization. Europium (Eu) complex dyes with different luminescent lifetimes ranging from microseconds to seconds were used to demonstrate and evaluate the principle of V-chopper on a 3D-printed smartphone microscopy platform. A convolutional neural network (CNN) model was developed to automatically distinguish the gated images in different decay cycles with an accuracy of >99.5%. The current smartphone V-chopper system can detect lifetime down to ∼75 µs utilizing the default phase shift between the smartphone video rate and excitation pulses and in principle can detect much shorter lifetimes by accurately programming the time delay. This V-chopper methodology has eliminated the need for the expensive and complicated instruments used in traditional time-resolved detection and can greatly expand the applications of time-resolved lifetime technologies.

Luminescent properties of Eu (III) complexes with carboxylate ligands and their light conversion films

This study reports the synthesis and characterization of four europium (III) complexes with different carboxylate ligands, namely 2-pyridine-acrylic acid (H2-PA), 2-pyridine-carboxylic acid (HPic), benzoic acid (HBen), and cinnamic acid (HCin), as well as a binuclear europium-lanthanum complex with HCin as the only ligand. The obtained complexes and the light conversion films prepared from them were extensively characterized by various techniques, including elemental analysis, infrared spectroscopy (IR), X-ray single crystal diffraction, thermogravimetric analysis (TGA), and fluorescence spectroscopy. Efforts were made to systemically investigate the structural, coordination, photophysical, and thermal properties of the luminescent materials, and elucidate the correlations between the ligand triplet energy levels and the luminescent properties of the complexes. The results reveal that the introduction of LaIII cannot only enhance the luminescent intensity of the light conversion agent and corresponding film, but also have obvious effect on enhancing the ultraviolet aging resistance of the light conversion film. Moreover, the proper doping concentration (0.5%) of the EuIII complex La-Eu-Cin in film may better balance the properties and cost.

Study on the structural and photophysical properties of N-acyl amino acid europium complexes

In this paper, a series of acyl amino acid europium complexes (Eu[CH3(CH2CH2)nCONHCH(CH3)COO]3, n = 0 ∼ 5) were synthesized using N-acyl amido alanine as ligands, and their structures and photophysical properties were studied.The structural and functional group information of europium complexes was obtained by elemental analysis, as well as infrared and hydrogen nuclear magnetic spectral analysis (1H NMR). The theoretical structure of the complexes was obtained by density functional theory (DFT) calculations; the theoretical structure of the complex was shown to be reliable by the comparison of theoretical and experimental vibrational and 1H NMR spectra. Additionally, the photophysical properties of the solid complexes at room temperature were determined by analysis of Ultraviolet–visible spectroscopy(UV–vis) and luminescence spectra. From the test results, it can be seen that the complex had good light absorption capacity in the range of 200–––300 nm; By comparison of the luminescence intensities of the complexes and EuCl3 proved that acyl amino acid ligands played a role in sensitizing Eu3+ characteristic luminescence. In addition, the effect of solution concentration on fluorescence performance has been studied. It can be inferred that complexes with longer carbon chains are less prone to aggregation in solution (increasing repulsive forces with increasing hydrophobicity), and the concentration, where fluorescence quenching occurs, is higher. Moreover, the solvent effect on the luminescence performance of the complexes was investigated by testing the luminescence spectrum of the complexes with different carbon chain lengths in a methanol solution(0.01 mol/L). Finally, the variable temperature spectral analysis provided information on the temperature-dependent variation of the luminescence properties of the complexes. The fluorescence performance of complexes with different carbon chain lengths that having different changing trends with temperature, with long carbon chain complexes exhibiting better high-temperature fluorescence stability.

X-ray structure, chelation enhanced fluorescence effect, thermal and redox properties of a new europium(III) complex based on bioactive naphthoquinone

The synthesis of metal complexes containing natural naphthoquinones has been highlighted due to their interesting electrochemical and spectroscopic properties, which may have a primordial influence on their pharmacological bioactivities. Simultaneously, processes of interaction of lanthanoid ions with organic ligands indicate the formation of coordination compounds that have marked luminescent properties of technological and medical diagnostic interest. Thus, this work describes the synthesis, characterization, and study of the properties of a new lawsone-EuIII metal complex, including the structural determination by XRD and the thermal, redox, and luminescent properties. The nine-coordinated complex exhibits a tri-hooded trigonal prismatic geometry, in which the metal ion is bound to nine oxygen atoms from three lawsone molecules and three water molecules, and the molecular structure still has approximately four water molecules as solvates, thus constituting [EuIII(C10H5O3)3(H2O)3].4H2O (FW = 797.49 g mol−1). The average CO and CC bond lengths indicate that naphthoquinone is coordinated in its anionic form, while the structural conformation shows intermolecular hydrogen interactions, which form interesting water channels. Thermal analyzes provided information regarding the decomposition behavior of the compound and its thermodynamic stability involving endothermic and exothermic processes. Electrochemical studies of the complex show that the processes associated with the ligand are shifted, with concomitant reduction of the Eu3+ ion. This new rearrangement is also responsible for differences in electronic transitions, such as the effect of increasing luminescence intensity (CHEF effect), and the phenomenon occurs through the antenna-like intramolecular interaction of the lawsonate anion with the europium(III) ion.

Eco-friendly strategy for synthesizing europium-complex-based hybrid materials using bifunctional hydroxyapatite

Synthesizing lanthanide complexes and their hybrid materials often involves the utilization of hazard base reagents to neutralize the protons generated in coordination reactions. Here, we propose for the first time a green and facile route to synthesize europium-complex-based hybrid materials by using micrometer-sized hydroxyapatite (HAP). Simultaneous formations of the europium complex and monetite took place after the reaction. Not only did HAP function as an eco-friendly alkaline reagent, but it also acted as a matrix to disperse the europium complexes. The quantum yield and lifetime of the as-synthesized hybrid materials are comparable to that of pure europium complex prepared by using traditional base reagents. Furthermore, versatile applications of the hybrid materials are also demonstrated in our proof-of-concept experiments, including bone tissue engineering, luminescent toys, and portable luminescent chalks. Notably, the proposed eco-friendly strategy is also applicable to other types of lanthanide-complexes-based hybrid materials.

Color Tunable Emission and Oxygen Sensing from a Discrete Europium−Pyrene Assembly

AbstractWe report the synthesis of a new pyrene, dipicolinic acid‐based ligand (L1H) and its corresponding multi‐emissive and multifunctional europium complex [Eu(L1)3] that is capable of single component color switchable emission from red to blue and also white. At high concentration (10 mM) the single component system results in near pure white emission (CIE coordinates x,y=0.329, 0.324). Furthermore, the system showed ratiometric oxygen sensing with oxygen significantly quenching the pyrene centered emission but not the Eu3+ emission, resulting in an overall emission color change from blue to red on increasing oxygen content.

Synthesis of a europium complex with ultrahigh quantum yield and its application as an invisible luminescent additive in pigments for preservation of cultural relics

A europium coordination compound [Eu2(ppip)2(PhCOO)6] (ppip is 1,2-diphenylimidazo[4,5-f][1,10]phenanthroline) has been synthesized and structurally characterized. In this symmetric dinuclear complex of octa-coordinated Eu(III) atom, both hanging phenyl rings in the ppip are twisted dramatically from the imidazophenanthroline part, leading to strong edge-to-face (T-type) C–H∙∙∙π interaction. This pale yellow stable complex possesses an ultrahigh luminescence quantum yield (84.2 ± 0.2%) under excitation at 365 nm, and hence is explored to be utilized in the preservation pigments for traditional Chinese paintings as an luminescent additive, which looks invisible under normal light, but exhibits bright red luminescence under UV excitation at a rather low percentage (0.02% wt).

Complexation of Europium(III) with Acetylacetone and Trialkylbenzylammonium in Extraction Systems According to Luminescent Spectroscopy Data

Complexation of Europium(III) with Acetylacetone and Trialkylbenzylammonium in Extraction Systems According to Luminescent Spectroscopy Data

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.