Photophysical Properties of a Novel Organic–Inorganic Hybrid Material: Eu(III)-β-Diketone Complex Covalently Bonded to SiO2/ZnO Composite Matrix

In this article, dibenzoylmethane (DBM) was first grafted with the coupling reagent 3-(triethoxysilyl)-propyl isocyanate (TESPIC) to form precursor DBM–Si, and ZnO quantum dot was modified with 3-mercaptopropyltrimethoxysilane (MPS) to form SiO₂/ZnO nanocomposite particle. Then the precursor DBM–Si and the terminal ligand 1,10-phenthroline (phen) were coordinated to Eu³⁺ion to obtain ternary hybrid material phen–Eu–DBM–SiO₂/ZnO after hydrolysis and copolycondensation between the tetraethoxysilane (TEOS), water molecules and the SiO₂/ZnO network via the sol–gel process. In addition, for comparison, the binary hybrid material with SiO₂/ZnO network and ternary hybrid material with pure Si–O network were also synthesized, denoted as Eu–DBM–SiO₂/ZnO and phen–Eu–DBM–Si, respectively. The results reveal that hybrid material with SiO₂/ZnO network phen–Eu–DBM–SiO₂/ZnO exhibits the stronger red light, the longer lifetimes and higher quantum efficiency than hybrid material with pure Si–O network phen–Eu–DBM–Si, suggesting that SiO₂/ZnO is a favorable host matrix for the luminescence of rare earth complexes.     

Lanthanide (Eu3+, Tb3+) Centered Mesoporous Hybrids with 1,3‐Diphenyl‐1,3‐Propanepione Covalently Linking SBA‐15 (SBA‐16) and Poly(methylacrylic acid)

1,3‐Diphenyl‐1,3‐propanepione (DBM)‐functionalized SBA‐15 and SBA‐16 mesoporous hybrid materials (DBM‐SBA‐15 and DBM‐SBA‐16) are synthesized by co‐condensation of modified 1,3‐diphenyl‐1,3‐propanepione (DBM‐Si) and tetraethoxysilane (TEOS) in the presence of Pluronic P123 and Pluronic F127 as a template, respectively. The as‐synthesized mesoporous hybrid material DBM‐SBA‐15 and DBM‐SBA‐16 are used as the first precursor, and the second precursor poly(methylacrylic acid) (PMAA) is synthesized through the addition polymerization reaction of the monomer methacrylic acid. These precursors then coordinate to lanthanide ions simultaneously, and the final mesoporous polymeric hybrid materials Ln(DBM‐SBA‐15)₃PMAA and Ln(DBM‐SBA‐16)₃PMAA (Ln=Eu, Tb) are obtained by a sol‐gel process. For comparison, binary lanthanide SBA‐15 and SBA‐16 mesoporous hybrid materials (denoted as Ln(DBM‐SBA‐15)₃ and Ln(DBM‐SBA‐16)₃) are also synthesized. The luminescence properties of these resulting materials are characterized in detail, and the results reveal that ternary lanthanide mesoporous polymeric hybrid materials present stronger luminescence intensities, longer lifetimes, and higher luminescence quantum efficiencies than the binary lanthanide mesoporous hybrid materials. This indicates that the introduction of the organic polymer chain is a benefit for the luminescence properties of the overall hybrid system. In addition, the SBA‐15 mesoporous hybrids show an overall increase in luminescence lifetime and quantum efficiency compared with SBA‐16 mesoporous hybrids, indicating that SBA‐15 is a better host material for the lanthanide complex than mesoporous silica SBA‐16.     

Hybrid materials of SBA-16 functionalized by rare earth (Eu, Tb) complexes of modified β-diketone (TTA and DBM): Covalently bonding assembly and photophysical properties

Novel mesoporous SBA-16 type of hybrids TTA-S16 and DBM-S16 were synthesized by co-condensation of modified β-diketone (TTA-Si and DBM-Si, DBM=1,3-diphenyl-1,3- propanepione, TTA=2-thenoyltrifluoroacetone) and tetraethoxysilane (TEOS) in the presence of Pluronic F127 as template, which were confirmed by FTIR, XRD, ²⁹Si CP-MAS NMR, and N₂ adsorption measurements. Novel organic-inorganic mesoporous luminescent hybrid containing RE³⁺ (Eu³⁺, Tb³⁺) complexes covalently attached to the functionalized ordered mesoporous SBA-16 (TTA-S16 and DBM-S16), which were designated as bpy-RE-TTA-S16 and bpy-RE-DBM-S16, were obtained by sol-gel process. The luminescence properties of these resulting materials were characterized in detail, and the results reveal that mesoporous hybrid material bpy-Eu-TTA-S16 present stronger luminescent intensities, longer lifetimes, and higher luminescent quantum efficiencies than the corresponding DBM-containing materials bpy-Eu-DBM-S16, while bpy-Tb-DBM-S16 exhibit the stronger characteristic emission of Tb³⁺ and longer lifetime than the corresponding TTA-containing materials bpy-Tb-TTA-S16.     

介孔氧化硅孔径尺寸对Eu(Ⅲ)配合物的影响

分别以十六烷基三甲基溴化铵(CTAB)和聚乙氧基-聚丙氧基-聚乙氧基三嵌段共聚物(P123)为模板剂、正硅酸乙酯(TEOS)为硅源，采用水热法合成了有序介孔分子筛MCM-41和SBA-15。选择Eu(DBM)₃phen为客体，有序介孔氧化硅MCM-41和SBA-15为载体，分别在氯仿中进行分子组装，制备出具有较强发光性能的介孔复合材料Eu(DBM)₃phen/APTES-MCM-41(EAM)和Eu(DBM)₃phen/APTES-SBA-15(EAS)。采用XRD、TEM、N₂吸附-脱附和荧光光谱等对产物的结构与性能进行了分析。结果表明，Eu(DBM)₃phen组装进有序介孔氧化硅的孔道中后，发光纯度提高。而且孔径越小，发光纯度越高。选用较大孔径的SBA-15为载体，在不显著影响发光纯度的同时，可以获得较高的发光强度。     

Synthesis, characterization, and near-infrared luminescent properties of the ternary thulium complex covalently bonded to mesoporous MCM-41

The crystal structure of a ternary Tm(DBM)₃phen complex (DBM=dibenzoylmethane; phen=1, 10-phenanthroline) and the synthesis of hybrid mesoporous material in which the complex covalently bonded to mesoporous MCM-41 are reported. Crystal data: Tm(DBM)₃phen C₅₉H₄₇N₂O₇Tm, monoclinic, P21/c, a=19.3216(12) Å, b=10.6691(7) Å, c=23.0165(15) Å, α=90°, β=91.6330(10)°, γ=90°, V=4742.8(5) Å³, Z=4. The properties of the Tm(DBM)₃phen complex and the corresponding hybrid mesoporous material [Tm(DBM)₃phen-MCM-41] have been studied. The results reveal that the Tm(DBM)₃phen complex is successfully covalently bonded to MCM-41. Both Tm(DBM)₃phen complex and Tm(DBM)₃phen-MCM-41 display typical near-infrared (NIR) luminescence upon excitation at the maximum absorption of the ligands, which contributes to the efficient energy transfer from the ligands to the Tm³⁺ ion, an antenna effect. The full width at half maximum (FWHM) centered at 1474 nm in the emission spectrum of Tm(DBM)₃phen-MCM-41 is 110 nm, which is the potential candidate of broadening amplification band from C band (1530-1560 nm) to S⁺ band (1450-1480 nm) in optical area.     

Hydrothermal synthesis, physical characterization and photoluminescence of homologous-SBA-15 fabricated with Eu

Two series of Eu³⁺-doped homologous-SBA-15 materials (abbreviated as MPTMS-SBA-15: Eu³⁺ and CTMS-SBA-15: Eu³⁺) have been synthesized by a hydrolysis-controlled technology, in which two novel silane crosslinking reagents (3-(methacryloyloxy) propyltrimethoxysilane (MPTMS) and 3-(chloropropyl) trimethoxysilane (CTMS)) are used as silicate precursor instead of traditional tetraethoxysilane (TEOS). It can be found that the different silicate precursors with different functional groups have influence on the physical properties of the corresponding homologous materials. In comparison to the pure SBA-15, the BET surface area and pore size of the modified mesoporous materials have been changed. Finally, the characteristic luminescence is observed for the ⁵D₀ → ⁷F_J (J = 0, 1, 2) transition of Eu³⁺ ion, suggesting that these kind of homologous-SBA-15 materials are potential host for the luminescence of Eu³⁺, whose excitation energy can be quenched by Eu³⁺ to some extent.     

Hybrid materials of MCM-41 functionalized by lanthanide (Tb, Eu) complexes of modified meta-methylbenzoic acid: Covalently bonded assembly and photoluminescence

Novel organic-inorganic mesoporous hybrid materials were synthesized by linking lanthanide (Tb³⁺, Eu³⁺) complexes to the mesoporous MCM-41 through the modified meta-methylbenzoic acid (MMBA-Si) using co-condensation method in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as template. The luminescence properties of these resulting materials (denoted as Ln-MMBA-MCM-41, Ln=Tb, Eu) were characterized in detail, and the results reveal that luminescent mesoporous materials have high surface area, uniformity in the ordered mesoporous structure. Moreover, the mesoporous material covalently bonded Tb³⁺ complex (Tb-MMBA-MCM-41) exhibits the stronger characteristic emission of Tb³⁺ and longer lifetime than Eu-MMBA-MCM-41 due to the triplet state energy of organic legend MMBA-Si matches with the emissive energy level of Tb³⁺ very well.     

Synthesis and Optical Properties of Europium‐Complex‐Doped Inorganic/Organic Hybrid Materials Built from Oxo–Hydroxo Organotin Nano Building Blocks

Hybrid materials doped with novel europium complexes were synthesized using PMMA‐co‐Sn₁₂Clusters (copolymers from oxohydroxo‐organotin dimethacrylate and methylmethacrylate) as the matrix material. Two types of hybrid materials were obtained: the physically doped product, PMMA‐co‐Sn₁₂Cluster/Eu(TTA)₃phen, and the grafted product, PMMA‐co‐Sn₁₂Cluster‐co‐[EuAA(TTA)₂phen] (TTA=2‐thenoyltrifluoroacetone, phen=phenanthroline and AA=acrylic acid). The hybrid materials exhibited characteristic luminescence of the Eu³⁺ ions, and also showed relative especial optical properties compared with samples just using PMMA as the matrix material. The PMMA‐co‐Sn₁₂Cluster matrix exhibited a high physical doping quantity of [Eu(TTA)₃phen], which can be attributed to the special structure of this kind of hybrid material. GPC (gel‐permeation chromatography), TGA (thermogravimetric analysis), SEM, ¹H NMR, ICP (inductively coupled plasma), ¹¹⁹Sn NMR, FTIR, and diffuse reflectance techniques were employed to characterize the structures and properties of these hybrid materials.     

Cofluorescence of dyes in nanoparticles from metal ion complexes with diketones

Nanoparticles (NPs) from diketonates of Al³⁺, Sc³⁺, In³⁺ and Ln³⁺ doped with dye molecules are synthesized. The appearance of sensitized fluorescence (cofluorescence) of dye molecules due to energy transfer from the ensemble of complexes forming NPs is revealed in aqueous solutions of these NPs. It is shown that the dye cofluorescence in NPs from Eu complexes occurs as a result of two distinct processes of energy transfer (ET) to dye molecules: from singlet levels of ligands and from Eu³⁺ ions. It is found that the efficiency of ET from Eu³⁺ ions to dyes in NPs from Eu(DBM)₃phen is one order of magnitude higher than the efficiency of ET from S₁-levels of ligands to dyes in NPs from Al complexes with the same ligands. It is shown that the excitation of dye molecules through ligands of NPs results in the enhancement of the intensity of their fluorescence by a factor of 1.5–2 orders of magnitude compared to the excitation of their own first band of absorption.     

Synthesis, photophysical and oxygen-sensing properties of a novel Eu complex incorporated in mesoporous MCM-41

A novel Eu³⁺ complex of Eu(DPIQ)(TTA)₃ (DPIQ=10H-dipyrido [f,h] indolo [3,2-b] quinoxaline, TTA=2-thenoyltrifluoroacetonate) was synthesized and encapsulated in the mesoporous MCM-41, hoping to explore an oxygen-sensing system based on the long-lived Eu³⁺ emitter. The Eu(DPIQ)(TTA)₃/MCM-41 composites were characterized by infrared spectra (IR), ultraviolet-visible (UV-vis) absorption spectra, small-angle X-ray diffraction (SAXRD), luminescence intensity quenching upon various oxygen concentrations, and fluorescence decay analysis. The results indicated that the composites exhibited the characteristic emission of the Eu³⁺ ion and the fluorescence intensity of ⁵D₀-⁷F₂ obviously decreased with increasing oxygen concentrations. The oxygen sensing properties of the composites with different loading levels of Eu(DPIQ)(TTA)₃ complex were investigated. A sensitivity of 3.04, a short response time of 7 s, and good linearity were obtained for the composites with a loading level of 20 mg/g. These results are the best reported values for optical oxygen-sensing materials based on Eu³⁺ complexes so far.     

Cooperative Sensitization Upconversion in Solution Dispersions of Co-Crystal Assemblies of Mononuclear Yb3+ and Eu3+ Complexes

Lanthanide upconversion luminescence in nanoparticles has prompted continuous breakthroughs in information storage, temperature sensing, and biomedical applications, among others. Achieving upconversion luminescence at the molecular scale is still a critical challenge in modern chemistry. In this work, we explored the upconversion luminescence of solution dispersions of co-crystals composed of discrete mononuclear Yb(DBM)₃Bpy and Eu(DBM)₃Bpy complexes (DBM: dibenzoylmethane, Bpy: 2,2′-bipyridine). The 613 nm emission of Eu³⁺ was observed under excitation of Yb³⁺ at 980 nm. From the series of molecular assemblies studied, the most intense luminescence was obtained for a 1 : 1 molar ratio of Yb³⁺ : Eu³⁺, resulting in a high quantum yield of 0.67 % at 2.1 W cm⁻². The structure and energy transfer mechanism of the assemblies were fully characterized. This is the first example of an Eu³⁺-based upconverting system composed of two discrete mononuclear lanthanide complexes present as co-crystals in non-deuterated solution.     

Effect of the Excitation of the 4f Shell of Eu(fod)3 on the Formation of Complexes with 1,10-Phenanthroline

The effect of the electronic excitation of the -diketonate Eu(fod)₃ (fod is 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedione-3,5) on complexation with 1,10-phenanthroline (phen) in benzene solutions was studied. The excitation of the f–f transitions of Eu³⁺ increased the stability of the Eu(fod)₃ · phen complex, thus providing direct evidence for the involvement of the 4f shell of Eu³⁺ in chemical bonding. The thermodynamic parameters of complexation were determined. The temperature quenching of Eu(fod)₃ · phen luminescence was studied.     

Synthesis, characterization, and luminescence properties of the ternary europium complex covalently bonded to mesoporous SBA-15

A novel mesoporous SBA-15 type of hybrid material (phen-SBA-15) covalently bonded with 1,10-phenanthroline (phen) ligand was synthesized by co-condensation of tetraethoxysilane (TEOS) and the chelate ligand 5-[N,N-bis-3-(triethoxysilyl)propyl]ureyl-1,10-phenanthroline (phen-Si) in the presence of Pluronic P123 surfactant as a template. The preservation of the chelate ligand structure during the hydrothermal synthesis and the surfactant extraction process was confirmed by Fourier transform infrared (FTIR) and (29)Si MAS NMR spectroscopies. SBA-15 consisting of the highly luminescent ternary complex Eu(TTA)(3)phen (TTA = 2-thenoyltrifluoroacetone) covalently bonded to a silica-based network, which was designated as Eu(TTA)(3)phen-SBA-15, was obtained by introducing the Eu(TTA)(3).2H(2)O complex into the hybrid materials via a ligand exchange reaction. XRD, TEM, and N(2) adsorption measurements were employed to characterize the mesostructure of Eu(TTA)(3)phen-SBA-15. For comparison, SBA-15 doped with Eu(TTA)(3).2H(2)O and Eu(TTA)(3)phen complexes and SBA-15 covalently bonded with a binary europium complex with phen ligand were also synthesized, and were named SBA-15/Eu(TTA)(3), SBA-15/Eu(TTA)(3)phen, and Eu-phen-SBA-15, respectively. The detailed luminescence studies on all the materials showed that, compared with the doping sample SBA-15/Eu(TTA)(3)phen and binary europium complex functionalized sample Eu-phen-SBA-15, the Eu(TTA)(3)phen-SBA-15 mesoporous hybrid material exhibited higher luminescence intensity and emission quantum efficiency. Thermogravimetric analysis on Eu(TTA)(3)phen-SBA-15 demonstrated that the thermal stability of the lanthanide complex was evidently improved as it was covalently bonded to the mesoporous SBA-15 matrix.     

基于稀土配合物的有机光盲型紫外探测器

使用二苯甲酰甲烷-二苯菲罗啉-铕(Eu(DBM)3BPhen)作为电子给体和[6,6]-苯基-C61-丁酸酸甲酯([60]PCBM)作为电子受体制备了一种新型的有机光盲型紫外探测器.在光强为2.1 mW cm-2且波长为360 nm的紫外光照射下,获得了26 mA W-1的响应度和9.1%的外量子效率,这是由于Eu(DBM)3BPhen的强紫外光吸收能力和长达300μs的激子寿命使得给受体界面处具有较高的激子解离率.在把[60]PCBM掺入Eu(DBM)3BPhen后,观察到了明显的光致发光猝灭和光电导现象.由于材料较低的载流子迁移率和受陷激子的缓慢释放,在紫外光照射关闭后,观察到了较强的持续光电导现象.     

Synthesis, Crystal Structure and Optical Properties of Europium Trifluoroacetate Complexes with 1,10-Phenanthroline and 2,2-Bipyridine

Two europium trifluoroacetate complexes, Eu(CF₃COO)₃·phen ( 1 ) and Eu(CF₃COO)₃·bpy ( 2 ) (where phen=1,10‐phenanthroline, bpy=2,2′‐bipyridine), were synthesized and characterized by elemental analysis, Fourier transform infrared spectroscopy (FT‐IR), photoluminescence (PL) spectroscopy and thermogravimetric analysis (TA). Single‐crystal X‐ray structure has been determined for the complex [Eu₂(CF₃COO)₆·(phen)₃·(H₂O)₂]·EtOH. The crystal structure of [Eu₂(CF₃COO)₆·(phen)₃·(H₂O)₂]·EtOH shows that two different coordination styles with europium ions coexist in the same crystal and have entirely different coordination geometries and numbers. This crystal can be considered as an 1:1 adduct of [Eu(CF₃COO)₃·(Phen)₂·H₂O]·EtOH (9‐coordination part) and Eu(CF₃COO)₃·phen·H₂O (8‐coordination part). The excitation spectra of the two complexes demonstrate that the energy collected by "antenna ligands" is transferred to Eu³⁺ ions efficiently. The room‐temperature PL spectra of the complexes are composed of the typical Eu³⁺ ions red emission, due to transitions between ⁵D₀→⁷F_J(J=0→4). The lifetimes of ⁵D₀ of Eu³⁺ in the complexes were examined using time‐resolved spectroscopic analysis, and the lifetime values of Eu(CF₃COO)₃·phen and Eu(CF₃COO)₃·bpy were fitting with bi‐exponential (2987 and 353 µs) and monoexponential (3191 µs) curves, respectively. In order to elucidate the energy transfer process of the europium complexes, the energy levels of the relevant electronic states had been estimated. The thermal analyses indicate that they are all quite stable to heat.     

Photoreduction of Europium (III) in Sol-Gel Derived Inorganic-Organic Hybrid Materials

Eu²⁺-doped inorganic-organic hybrid materials, which are potentially suitable for a tunable laser in the near ultra violet and blue region, were prepared through the photoreduction of Eu³⁺ ions in the materials under the irradiation of the fourth harmonic wave light (266 nm) of the Nd:YAG laser. The hybrid materials doped with Eu³⁺ ions were prepared from Si(OCH₃)₄, CH₃Si(OCH₃)₃, EuCl₃ and chloropropyltrimethoxysilane (CPTM). After the prehydrolized silica sol was added to the Eu³⁺-containing solution, Eu³⁺-doped transparent inorganic-organic hybrid material was obtained by drying at 50°C. The emission peak around 450–475 nm due to the charge transfer transition (5d-4f) of Eu²⁺ ions increased with the laser irradiation time. Eu³⁺ ions were effectively photoreduced to Eu²⁺ ions in pore-free materials prepared at high CPTM to Eu³⁺ ratios. Eu²⁺ ions were generated by the photodecomposition of the bond between Eu³⁺ and Cl (Cl^– or Cl(CH₂)₃ in CPTM).     

Adducts of lanthanide β-diketonates with 2,4,6-tri(2-pyridyl)-1,3,5-triazine: Synthesis,structural characterization,and photoluminescence studies

Adducts of lanthanide β-diketonates of the general formula LnL₃(TPTZ) were synthesized and structurally characterized by single crystal X-ray diffraction [Ln = Eu³⁺, Tb³⁺, Er³⁺; L is the conjugate base of dibenzoylmethane (DBM), 1-benzoylacetone (BA), thenoyltrifluoroacetone (TTA), or 4,4,4-trifluoro-1-phenyl-1,3-butanedione (BTFA); TPTZ = 2,4,6-tri(2-pyridyl)-1,3,5-triazine, a rigid Lewis base with a large π system]. The lanthanide ion in each of these complexes is nonacoordinate with six β-diketonate oxygen atoms and three TPTZ nitrogen atoms, forming a coordination polyhedron best describable as a monocapped square antiprism. Characteristic red, green, and near infrared luminescence was observed for the Eu³⁺, Tb³⁺, and Er³⁺ complexes, respectively. All complexes showed significantly enhanced luminescence quantum yields when compared with the corresponding aqua analogues, with one of the Eu³⁺ complexes displaying a quantum yield of 69.7% in chloroform.     

Synthesis and Luminescence of Eu‐N2,N6‐Bis(2‐hydroxyethyl)pyridine‐2,6‐dicarboxamide Complexes Containing Mesoporous Material

Ligand N²,N⁶‐bis(2‐hydroxyethyl)pyridine‐2,6‐dicarboxamide (L=BHPC) was synthesized and used to construct lanthanide‐based mesoporous material Eu‐L‐MCM‐41. In the structure of resulting Eu‐L‐MCM‐41, Eu³⁺ was chelated by BHPC, and the Eu‐L complexes were anchored into the forming MCM‐41 host by the reaction between the hydroxyl group and active Si‐OH. The mesoporous material Eu‐L‐MCM‐41 was characterized by UV, IR, small‐angle X‐ray diffraction (SAXRD) patterns, nitrogen adsorption/desorption isotherms, TGA and fluorescence spectra. The results indicate that ligand and Eu³⁺ have been introduced into the MCM‐41 host, and Eu‐L‐MCM‐41 exhibits characteristic luminescence of Eu³⁺.     

Synthesis,structure and luminescence properties of two novel lanthanide complexes with 2-fluorobenzoic acid and 1,10-phenanthroline

Two lanthanide complexes with 2-fluorobenzoate (2-FBA) and 1,10-phenanthroline (phen) were synthesized and characterized by X-ray diffraction. The structure of each complex contains two non-equivalent binuclear molecules, [Ln(2-FBA)₃?·?phen?·?CH₃CH₂OH]₂ and [Ln(2-FBA)₃?·?phen]₂ (Ln?=?Eu (1) and Sm (2)). In [Ln(2-FBA)₃?·?phen?·?CH₃CH₂OH]₂, the Ln³⁺ is surrounded by eight atoms, five O atoms from five 2-FBA groups, one O atom from ethanol and two N atoms from phen ligand; 2-FBA groups coordinate Ln³⁺ with monodentate and bridging coordination modes. The polyhedron around Ln³⁺ is a distorted square-antiprism. In [Ln(2-FBA)₃?·?phen]₂, the Ln³⁺ is coordinated by nine atoms, seven O atoms from five 2-FBA groups and two N atoms of phen ligand; 2-FBA groups coordinate Ln³⁺ ion with chelating, bridging and chelating-bridging three coordination modes. The polyhedron around Ln³⁺ ion is a distorted, monocapped square-antiprism. The europium complex exhibits strong red fluorescence from ⁵D₀?→?⁷F _j ( j?=?1–4) transition emission of Eu³⁺.     

Synthesis and photoluminescence of Eu(III) and Tb(III) complex compounds containing anions of 4-CF3C6F4COOH and 4-(CF3)2CFC6F4COOH acids

Hydrates of Eu(III) and Tb(III) salts with anions (L) 4-CF₃C₆F₄COO^? and 4-(CF₃)₂CFC₆F₄COO^?, and also mixed-ligand complexes Ln(phen)(L)₃ were obtained. The compounds show red and green photoluminescence characteristic of Eu³⁺ and Tb³⁺ ions, respectively, in the visible region of spectrum. The intensity of the photoluminescence of the complexes containing 1,10-phenanthroline is much higher than that of compounds containing water. It is connected with sensitizing properties of phen in relation to Eu³⁺ and Tb³⁺ ions.