Eu Complexes Research Articles

Influence of Hydroxycoumarin Substituents on the Photophysical Properties of Chiroptical Tb(III) and Eu(III) Complexes.

In this article, the synthesis, density functional theory (DFT) structural characterization, and spectroscopic investigation of chiral and heteroleptic Tb(III) and Eu(III) complexes are presented. These molecules are characterized by two different ligands: the enantiopure N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetic acid (H2bpcd) and a hydroxycoumarin-based ligand bearing different substituents in C(3) position (i.e., acetyl group in Coum, ethyl ester in CoumA, secondary and tertiary amides in CoumB and CoumC, respectively). The coumarin ligands exhibited different luminescence sensitization efficiency toward Tb(III) and Eu(III) ions in the related complexes of chemical formula [Ln(bpcd)(Coum)], [Ln(bpcd)(CoumA)], [Ln(bpcd)(CoumB)], [Ln(bpcd)(CoumC)]. Through theoretical calculations of intramolecular energy transfer (IET) processes (ligand-to-metal) in Eu(III) and Tb(III) complexes, along with quantum yield calculations, we provide a reasonable explanation for the observed differences in their luminescence properties. The nature of the coumarin ligand also affects the chiroptical properties of the Tb(III) complexes [i.e., circularly polarized luminescence (CPL) and electronic circular dichroism (ECD)].

Exploring the influence of emissive centers in mono and dinuclear europium(III) complexes for advance lighting applications: Synthesis, characterization and computational modelling

The combination of 4,4,4-trifluoro-1-phenyl-1,3-butanedione (TFPB) and pyrazine (pyz) with Eu3+ ions results in the formation of two distinct types of complexes, characterized by general formulae [Eu(TFPB)3(L)2] (here, L is either H2O or pyrazine) and [(Eu(TFPB)3)2pyz]. The impact of surrounding environment on the photophysical properties of synthesized complexes was thoroughly examined. Photoluminescence (PL) analysis revealed the dominance of electric dipole (ED) transition (5D0→7F2) in these complexes. Theoretical calculations via Judd-Ofelt analysis were also performed. These complexes exhibit visible luminescence in both solid and solvated forms. Notably, the luminescence intensity of prepared dinuclear complex is found to be manifolds greater than its mononuclear analogues, affirming the contribution of both metal centers towards emission intensity. Furthermore, the absence of ligand centered emission in prepared complexes suggests the effective energy transfer from coordinated moieties to metal center. CIE color coordinates of prepared Eu(III) complexes, in both solid and solution media, exhibited intense red emission. DFT calculations were conducted to elucidate the distribution of electronic density in synthesized complexes. Additionally, a comprehensive analysis of these complexes, including IR, UV, NMR, thermogravimetry and cyclic voltammetry was conducted.

Self-assembly aggregation-induced emission from Eu (III) complexes with o-hydroxy-benzophenone ligands

In this work, europium (III) complexes were synthesized by using different o-hydroxy-benzophenone ligands, namely 2-hydroxy-4-octyloxybenzophenone (HL1), 4-allyloxy-2-hydroxybenzophenone (HL2) and 2-hydroxy-4-methoxybenzophenone (HL3). The structures and optical properties of the EuIII complexes E1, E2 and E3 were characterized by elemental analysis, infrared/fluorescence spectroscopy and mass spectrometry. The aggregation-induced emission properties from E1, E2 and E3 were systematically investigated in the acetone/water binary mixtures. At the same time, the corresponding agglomeration behavior and self-assembly structures in the EuIII complex system was confirmed through scanning electron microscopy. Excellent luminescent performance was illustrated in sample of E1 (the luminescence quantum yield of 21.36 % in solid state) which should be attributed to the aggregation-induced emission from better self-assembly behavior with longer carbon chain in ligand. The results of ultraviolet aging resistance from E1 reveal that the self-assembly behavior could not only improve the aggregation-induced emission performance, but also enhance the photostability of EuIII complex compared with the traditional β-diketone EuIII complex. This discovery may provide a facile strategy to design and prepare more promising rare earth complexes with good luminescence properties and strong photostability for application in solid state.

Complexation of Trivalent Lanthanides with Hexaalkyl Nitrilotriacetamides into Methylimidazolium-Based Ionic Liquids: Spectroscopic, Electrochemical, Calorimetric, and Theoretical Insights.

Exothermic, spontaneous inner-sphere complexation of trivalent lanthanides with N,N,N',N',N″,N″-hexaalkyl-substituted nitrilotriacetamides (HRNTAs) into 1-hexyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (C6mim NTf2) is reported with a predominant presence of ML and ML2 complexes having complexation constants, β1Eu 3.10 ± 0.02 ,β1Nd 2.67 ± 0.03 and β2Eu 5.22 ± 0.04, β2Nd 4.95 ± 0.02, respectively, for the n-butyl-substituted HRNTA (HBNTA); while those for the n-hexyl derivative (HHNTA) are β1Eu 4.27 ± 0.03, β1Nd 3.71 ± 0.03 and β2Eu 7.70 ± 0.03, β2Nd 7.18 ± 0.04, respectively. HHNTA shows better complexing ability; whereas the stronger complexation of the Nd3+ over Eu3+ is attributed to the lanthanide contraction. Furthermore, the nature of the ionic liquid also influences the extent of complexation with the trend: C4mim NTf2 > C6mim NTf2 > C8mim NTf2, which follows the order of their dielectric constants. Judd-Ofelt parameters were calculated from photoluminescence data to get an idea about the symmetry of the Eu3+ complexes. Electrochemical investigations give diffusion coefficient values of 1.17 × 10-7 and 8.26 × 10-8 cm2/s for the Eu3+ complexes of HBNTA and HHNTA, respectively. Changes in the spectral characteristics and peak positions are evidenced in the FTIR spectra on the complexation of Eu3+ with the HRNTA ligands in C6mim NTf2. Structure optimization for the complexes was performed by DFT computations.

Solution and solid state structures of lanthanides(III) and uranyl(II) complexes of tripodal tris(2-pyridyl)-containing ligand on Ph3P(O) platform

Reaction of tris[2-(2′-pyridylmethoxy)phenyl]phosphine oxide (L) with f-element nitrates resulted in 1:1 complexes. The isolated complexes of ligand L with La(III), Eu(III), Tb(III), and U(VI) nitrates, and with La(III) chloride were studied in the solid state and solution by IR, Raman, and NMR spectroscopy, X-ray analysis, and also DFT calculations. Composition and structure of the complexes vary with lanthanide cation radius. According to the data of elemental analysis, vibrational spectroscopy, and X-ray diffraction, the ligand is coordinated in tridentate mode in crystalline La(III) and solid Eu(III) complexes: [Ln(OPO,N,Oeth-L)(H2O)(O,O-NO3)3], and in monodentate mode in crystalline complex [Tb(OPO-L)(H2O)2(O,O-NO3)3]. Nitrogen atoms of pyridine fragments of the ligand not involved in coordination produce intra- and intermolecular H-bonds with coordinated water molecules in the second coordination sphere of Ln(III). According to IR, NMR spectrometry, and DFT calculations, the structure of coordination polyhedron of the main species of Ln(III) complexes in acetonitrile solutions is retained including coordination of one of pyridine fragments in the second coordination sphere: [Ln{OPO,N,(N*),Oeth-L}(H2O)(O,O-NO3)3] and [Tb{OPO,(N*)-L}(H2O)2(O,O-NO3)3], where Ln = La, Eu, and N* is the nitrogen atom of pyridine fragment producing intramolecular H-bond with coordinated water molecule. According IR and Raman spectroscopy, ligand L is coordinated in bidentate mode in solid complex [UO2(OPO,N-L)(O,O-NO3)], and uncoordinated nitrogen atoms remain free. Solution structure of uranyl complex is labile and depends on solvent nature. Equilibria of complex species with variable coordination of nitrate ions, ligand L, and with probable involvement of water take place in CD3CN and CDCl3 solutions. Photophysical properties of the prepared Eu(III) and Tb(III) complexes were studied. The preliminary assessment of extraction properties of compound L was made. Stability of studied compounds in acetonitrile solutions was examined, and the structure of one of protolysis product of Eu(III) complex, [Eu(LH)(H2O)(NO3)4], was established by micro-IR and X-ray analysis.

Synthesis of Bis(2,6-Diadamantyl Aryloxide) Ln(II) Complexes of Samarium, Europium, and Ytterbium and Their Ln(III) Precursors.

The syntheses of Ln(II) bis(aryloxide) complexes of Sm, Eu, and Yb have been examined with the bulky aryloxide ligand (OC6H2-2,6-Ad2-4-tBu)1- [(OAr*)1-; Ad = 1-adamantyl]. These LnII(OAr*)2(THF)2 complexes were pursued for comparison with the tris(aryloxide) Ln(II) complexes [LnII(OAr*)3]1- (Ln = La, Ce, Nd, Gd, Dy, and Lu), which have 4fn5d1 electron configurations, and with 4f14 [YbII(OAr*)3]1-. Although the Ln(II) chemistry of Sm, Eu, and Yb is often similar since they all adopt 4fn+1 electron configurations, their chemistry is surprisingly diverse with (OAr*)1-. Reactions of LnIII2(THF)2 with KOAr* in THF form the bis(aryloxide) Ln(II) complexes LnII(OAr*)2(THF)2, 1-Ln, that were characterized by X-ray diffraction for 1-Sm and 1-Yb, but crystals of 1-Eu have been elusive. Reduction of the tris(aryloxide) Sm(III) complex, SmIII(OAr*)3, 2-Sm, prepared from SmIII(NR2)3 (R = SiMe3) and HOAr* in refluxing toluene, generated the bis(aryloxide) complex, 1-Sm, and KOAr* rather than a Sm analogue of [YbII(OAr*)3]1-. Reduction of EuIII(OAr*)3, 2-Eu, prepared from EuCl3 with KOAr* in THF, caused an immediate dark blue-purple to bright red-orange color change, but crystals of the product were elusive. Neither reduction of TmIII(OAr*)3, 2-Tm, nor the reaction of TmIII2(DME)3 with KOAr* provided crystalline Tm(II) complexes.

Quantum–Chemical Study of the Photophysical Behavior of Mesogenic Europium(III) Complexes with β‐Diketones and Lewis Bases

AbstractMetal‐containing liquid crystals such as Ln(III) complexes possess unique structural, liquid‐crystalline (LC), optical, and magnetic properties and represent modern cutting‐edge multifunctional materials. Application of mesogenic Ln(III) complexes is hindered by their nontrivial structure–property relationships. These relationships, in turn, depend on various factors, including insufficiently studied physicochemical processes. Although a proper Ln(III) element and the respective ligand environment are selected prior to synthesis of such complexes, the structural features of the coordination polyhedra, especially upon photoexcitation, are not uniquely defined. Therefore, this work focuses on the development of theoretical approaches to creating multifunctional materials represented by highly luminescent mesogenic Eu(III) complexes with β‐diketones and Lewis bases. The relationships between their structure, the parameters of Voronoi–Dirichlet polyhedra, the luminescence efficiency, and the LC properties were considered. The calculated excited states and intramolecular energy transfer rates were used to determine intramolecular energy transfer channels. The LC behavior of the studied materials was shown to mainly depend on the ligand environment, whereas their optical properties were found to be mostly governed by the coordination polyhedra.

Structural and Thermodynamic Analyses of the Complexation of Pr(III), Nd(III), and Eu(III) with Lactate for Simulating the TALSPEAK Process.

The complexation of Pr(III), Nd(III), and Eu(III) with lactic acid/lactate (HA/A-) in aqueous solution was reinvestigated using spectroscopic and potentiometric titrations. In addition to the well-confirmed 1:1, 1:2, and 1:3 complexes (LnA2+, LnA2 +, and LnA3), more attention was given to the arguable 1:4 species (LnA4 -) previously reported. With spectroscopic methods, the LnA4 - species was clearly identified in aqueous solutions, and the capability and limitation of the potentiometric method were evaluated and discussed. With the confirmed stability constants for the four complexes, a simulation of the TALSPEAK process (Trivalent Actinide Lanthanide Separation with Phosphorus-Reagent Extraction from Aqueous Complexes) was performed, clarifying the error caused by the previously missing 1:4 species. It was found that high concentrations of lactic acid/lactate (over 2 mol/L) slightly affect the extraction of Ln(III) in the TALSPEAK process, but it might not be accountable for the considerable difference between experimental results and predictions from the simulation using currently adapted model.

Sorption of trivalent europium Eu(III) by Na+-substituted bentonite: Mechanistic insight and stabilization effect

The sorption of Eu(III) by Na+-substituted bentonite (Na-bentonite) was investigated as a function of pH and NaNO3 concentration ([NaNO3]0). At pH < ∼7.5, Eu(III) sorption decreased with the increasing [NaNO3]0, whereas at pH > ∼7.5, it remained nearly complete, independent of [NaNO3]0. Our thermodynamic model indicated that the sorption at pH < ∼7.5 occurred via a combination of cation exchange and surface complexation, with the former diminishing as [NaNO3]0 increased. Meanwhile, the sorption at pH > ∼7.5 was primarily due to surface complexation. By X-ray diffraction, the incorporation of hydrated Eu(III) in the interlayers of montmorillonite increased its lattice spacing and crystallinity along the c-axis, where cation exchange was predominant. Also, Eu LIII-edge X-ray absorption spectroscopy revealed that the sample dominated by cation exchange had an absorption edge energy and coordination structure similar to aqueous Eu(III), indicating outersphere complex formation. In other cases, Eu(III) sorption was characterized by innersphere complexation, as indicated by increased covalency and the presence of more pronounced second coordination shells. Importantly, the analysis of dissolved Si and Al suggested that the increased stability of Na-bentonite was likely due to the surface complexation of Eu(III) with aluminol groups at the edges, especially at higher surface coverages. Given its high sorption capacity for Eu(III) and stabilization effect mediated by sorption, Na-bentonite could be serve as an effective backfill material and migration barrier for containing actinides in nuclear waste repositories.

Eu(III) complexes derived from 2-quinolinecarbohydrazide Schiff base ligand, relations between structure and luminescence properties

A series of Eu(III) complexes were obtained following the template condensation of 2-quinolinecarbohydrazide and 2,6-diacetylpyridine, namely: [Eu(H2pbqh)(NO3)3]·MeOH (1), [Eu(Hpqh)(NO3)3]·2MeCN (2), [Eu(H2pbqh)(SCN2)(MeOH)2](SCN) (3) and [Eu2(pbqh)2(NO3)2(H2O)2]·2.5MeOH (4). The structures of complexes and a new H2pbqh ligand (N',N'''-((1E,1′E)-pyridine-2,6-diylbis(ethan-1-yl-1-ylidene))bis(quinoline-2- carbohydrazides)) were elucidated by single-crystal X-ray diffraction. H2pbqh coordinate pentadentate ONNNO and forms mononuclear complexes 1 and 3. The bis-deprotonated ligand pbqh2- act as hexadentate/bridging mode generates the binuclear complex in 4. The partially condensed ligand Hpqh, tetradentate ONNO, was recorded in complex 2. The crystallographic results reveals that the coordinated H2pbqh/Hpqh ligands and Eu3+ cation form a planar structure in these complexes and nitrate anions coordinate chelate, completing the coordination sphere of Eu3+. The solid state photoluminescent emission was investigated highlighting the nitrate complexes 1 and 2 that exhibit red intense luminescence (λmax = 618 nm). Moreover, the computational calculations reveal different pathways of energy transfer from ligand to Eu3+ electronic states explaining the luminescent behavior.

Sm(Ⅲ), Gd(Ⅲ), and Eu(Ⅲ) complexes with 8-hydroxyquinoline derivatives as potential anticancer agents via inhibiting cell proliferation, blocking cell cycle, and inducing apoptosis in NCI-H460 cells.

Four lanthanide complexes with 8-hydroxyquinoline-2-aldehyde-2-hydrazinopyridine (H-L1), 8-hydroxyquinoline-2-aldehyde-2-hydrazimidazole (H-L2): [Sm(L1)2][Sm(L1)(NO3)3]·CHCl3·2CH3OH (1), [Gd(L1)2][Gd(L1)(NO3)3]·CHCl3·2CH3OH (2), [Sm(L2)(NO3)2]2·CH3OH (3), and [Eu(L2)(NO3)2]2·CH3OH (4) were synthesized and characterized. In vitro cytotoxicity evaluation showed that the ligands and four lanthanide complexes exhibited cytotoxicity to the five tested tumor cell lines. Among them, complex 1 showed the best antiproliferative activity against NCI-H460 tumor cells. Mechanistic studies demonstrated that complex 1 arrested the cell cycle of NCI-H460 cells in G1 phase and induced mitochondria-mediated apoptosis, which resulted in the loss of mitochondrial membrane potential, enhanced intracellular Ca2+ levels and reactive oxygen species generation. In addition, complex 1 affected the expression levels of intracellular apoptosis-related proteins and activated the caspase-3/9 in NCI-H460 cells. Therefore, complex 1 is a potential anticancer agent.

Synthesis, crystal structures, characterization and luminescent thermal stability of Eu(III) and Gd(III) complex

Two new dinuclear lanthanide complexes [Ln2(Hsal)3(NO3)6]·(C2H5N)3·nH2O (Ln = Gd, Eu) were synthesized with an aromatic carboxylic acid ligand (salicylate). Both complexes were extensively characterized by various techniques, including elemental analysis, infrared spectroscopy, powder X-ray diffraction, and X-ray single-crystal diffraction. The thermal behavior and photoluminescence properties of lanthanide complexes were investigated. It was found that the two complexes had good thermal stability even after heating at 180 °C for 1 h. Furthermore, the two complexes exhibit a unique luminescent thermal stability.

Interplay of Circularly Polarized Light with Molecular and Structural Chirality: Chiral Lanthanide Complexes and Cellulose Nanocrystals

AbstractThe interaction of circularly polarized (CP) light with chiral matter at different scales opens several possibilities of light manipulation in photonic and electronic devices. Here it is shown that in a multilayer architecture, it is possible to take advantage of the polarization‐selective reflection of the nematic arrangement of cellulose nanocrystals and the strong intrinsic CP luminescence (CPL) of the various bands of chiral Eu complexes. In this way, both the intrinsic CPL and total emission of the complex are modified depending on the enantiomer applied and on the detection geometry. This concept may apply for polarization control in electronic and photonic devices and polarized optical cavities.

Lanthanide-Dependent Photochemical and Photophysical Properties of Lanthanide-Anthracene Complexes: Experimental and Theoretical Approaches.

The structural, photophysical, and photochemical properties of Ln(depma)(hmpa)2(NO3)3 (Ln = La, Ce, Nd, Sm, Eu, Tb, Ho, Er, and Yb) complexes 1-Ln were investigated with a multidisciplinary approach involving synthesis, photocycloaddition-based crystal engineering, spectroscopic analytical techniques and quantum chemical ab initio calculations. Depending on the Ln3+ ion the isostructural 1-Ln complexes exhibit quite different behavior upon excitation at 350-400 nm. Some 1-Ln complexes (Ln = La, Ce, Sm, Tb, Yb) emit a broad and strong band near 533 nm arising from paired anthracene moieties, whereas others (Ln = Nd, Eu, Ho, Er) do not. 1-Eu is not emissive at all, whereas 1-Nd, 1-Ho, and 1-Er exhibit a Ln3+ based luminescence. Upon irradiation with 365 nm ultraviolet (UV) light 1-Ln (Ln = La, Ce, Sm, Tb, Yb) dimerize by means of a photochemically induced [4 + 4] cycloaddition of the anthracene moieties, whereas 1-Ln (Ln = Nd, Eu, Ho, Er) remain monomers. We propose three models, based on the matching of the energy levels between the Ln3+ ion and the paired or dimerized anthracene units in the energy-resonance crossing region, as well as on internal conversion-driven and intersystem crossing-driven energy transfer, which explain the Ln3+ ion regulated photophysics and photochemistry of the 1-Ln complexes.

Substituent effect induced circularly polarized luminescence enhancement of Eu(III) enantiomers

Circularly polarized luminescence (CPL) has received much attention in optical displays, information storage, and biological probes. Designing effective strategy to improve the CPL activities is significant for complex materials. Structural modification is a rational way which is seldom reported. In this work, three chiral binuclear Eu(III) complexes coordinated with different chiral Schiff base ligands were designed and synthesized. CPL performances of these Eu(III) complexes were substantially improved by polarity of substituents at the chiral carbon sites of the ligands, leading to a five-fold increase in the luminescence dissymmetry factor (glum). Additionally, three complexes exhibited similar luminescence properties with the characteristic peaks of Eu(III) ion, which can be rapidly quenched by Co(II) ion, allowing their further applications in anti-counterfeiting and sensors. Therefore, this work not only uncovers the relationship between the substituents of chiral ligand and the corresponding CPL properties of Eu(III) complexes to some extent, but also creates opportunities for design and synthesis of Eu(III) complexes with excellent CPL activity.

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.

Fabrication of POE/POE‐g‐PHEMA/EuFT light conversion films for photovoltaic modules

AbstractIn this paper, the rare earth europium complex Eu(FTFA)3TPPO2 (EuFT) was synthesized by using europium as the central ion, 4‐trifluoro‐1‐(2‐furanyl)‐1,3‐butanedione (FTFA) as the first ligand, and triphenylphosphine oxide (TPPO) as the second ligand. The structure was characterized by Fourier transform infrared spectroscopy (FTIR), and the photoluminescence process was investigated by UV and fluorescence spectra. The luminescent film was prepared by adding EuFT and the compatibilizer POE‐g‐PHEMA into the POE matrix, which can convert the UV light to the red light, and improve the photovoltaic conversion efficiency while reducing the effect of UV aging on the cell. Experimental results show that the complex can absorb UV light (200–400 nm) and emit red light (612 nm), the luminescent film also maintains good luminescence performance. The peel strength of POE/POE‐g‐PHEMA/EuFT film achieves 23.9 N cm−1，while that of POE film is 12.8 N cm−1. The silicon cell prepared by POE/POE‐g‐PHEMA/EuFT film also showed higher EQE in UV region, and its current density–voltage (J–V) curve revealed that Jsc increased from 33.05 to 34.25 mA/cm2, the conversion efficiency increased from 12.99% to 13.39%, and the relative efficiency increased by 3.08%. The rare earth europium complex effectively improved the photoelectric conversion efficiency of solar cells.

Unveiling the Versatility of Coumarin-Integrated with Phenanthroline/Thiabendazole-Based EuIII Complexes for Smart LEDs, Vapoluminescence, and Bioimaging Applications.

Narrow band red-emitting phosphors based on organo-Eu(III) complexes prove their energetic features with surprising performance in smart red/white LEDs, sensing, and biological fields. In this report, a series of unique Eu(III) complexes have been synthesized with coumarin integrated with a class of phenanthroline(Phen)/thiabendazole(TBZ) based ancillary ligands and dibenzoyl methane (DBM)/2-theonyl trifluoroacetone (TTA) as an anionic ligand. The computational study reveals that the TBZ/Phen-based neutral ligands are superior energy harvesters to those other reported analogue neutral ligands. All the Eu-complexes demonstrated outstanding red emission due to electric dipole (ED) transition (5D0 → 7F2) in solid, solution, and thin film with high quantum yield (QY). Theoretical analysis (TD-DFT) and experimental findings describe that the energy transfer (ET) from the ligand's triplet level to the Eu(III) ion is completely occurring. The Eu(III) complexes can potentially be used to fabricate intense hybrid white and red LEDs. All of the fabricated red LEDs revealed high luminous efficiency of radiation (LER) values. The fabricated blue LED based hybrid white LEDs displayed remarkable performance with a low correlated color temperature (5634 K), high color rendering index 88%, and CIE values (x = 0.33; y = 0.342) for 3Eu. By interaction with acid-base vapors, Eu-complexes displayed effectively alterable on-off-on luminescence. Further, cellular imaging shows that Eu-complexes can be a potential biomarker for cancer cell lines.

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.

Spectral Hole-Burning Studies of a Mononuclear Eu(III) Complex Reveal Narrow Optical Linewidths of the 5D0→7F0 Transition and Seconds Long Nuclear Spin Lifetimes.

Coordination complexes of rare-earth ions (REI) show optical transitions with narrow linewidths enabling the creation of coherent light-matter interfaces for quantum information processing (QIP) applications. Among the REI-based complexes, Eu(III) complexes showing the 5D0→7F0 transition are of interest for QIP applications due to the narrow linewidths associated with the transition. Herein, we report on the synthesis, structure, and optical properties of a novel Eu(III) complex and its Gd(III) analogue composed of 2,9-bis(pyrazol-1-yl)-1,10-phenanthroline (dpphen) and three nitrate (NO3) ligands. The Eu(III) complex-[Eu(dpphen)(NO3)3]-showed sensitized metal-centred emission (5D0→7FJ; J=0,1,2,3, 4, 5, or 6) in the visible region, upon irradiation of the ligand-centred band at 369 nm, with the 5D0→7F0 transition centred at 580.9 nm. Spectral hole-burning (SHB) studies of the complex with stoichiometric Eu(III) concentration revealed a narrow homogeneous linewidth (Γh) of 1.55 MHz corresponding to a 0.205 μs long optical coherence lifetime (T2opt). Remarkably, long nuclear spin lifetimes (T1spin) of up to 41 s have been observed for the complex. The narrow optical linewidths and long T1spin lifetimes obtained for the Eu(III) complex showcase the utility of Eu(III) complexes as tuneable, following molecular engineering principles, coherent light-matter interfaces for QIP applications.