Luminescence of Eu3+ and Tb3+ Complexes of Two Macrobicyclic Ligands Derived from a Tetralactam Ring and a Chromophoric Antenna

Two macrobicyclic ligands derived from an 18‐membered tetralactam ring and 2,2′‐bipyridine or 2,6‐bis(pyrazol‐1‐yl)pyridine moieties, 1 and 2 , respectively, form stable complexes with Gd^III, Eu^III, and Tb^III ions in aqueous solution. The ligand‐based luminescence is retained in the Gd^III cryptates, whereas this radiative deactivation is quenched in the Eu^III and Tb^III cryptates by ligand‐to‐metal energy transfer, resulting in the usual metal‐centered emission spectra. Singlet‐ and triplet‐state energies, emission‐decay lifetimes, and luminescence yields were measured. [Tb⊂ 1 ]³⁺ cryptate shows a long luminescence lifetime (τ=1.12 ms) and a very high metal luminescence quantum yield (Φ=0.25) in comparison with those reported in the literature for Tb³⁺ complexes sensitized by a bipyridine chromophore. By comparison to [Ln⊂ 1 ]³⁺, [Ln⊂ 2 ]³⁺ presents markedly lower luminescence properties, due to worse interaction between the 2,6‐bis(pyrazol‐1‐yl)pyridine unit and the metal ion. Moreover, the luminescent metal and the triplet ligand energy levels of [Eu⊂ 2 ]³⁺ do not match. The effects of H₂O molecules coordinated to the metal centre and of thermally activated decay processes on nonradiative deactivation to the ground‐state are also reported.     

A template-free solvothermal synthesis and photoluminescence properties of multicolor Gd2O2S:xTb3+, yEu3+ hollow spheres

The multicolor Gd₂O₂S:xTb³⁺, yEu³⁺ hollow spheres were successfully synthesized via a template-free solvothermal route without the use of surfactant from commercially available Ln (NO₃)₃·6H₂O (Ln = Gd, Tb and Eu), absolute ethanol, ethanediamine and sublimed sulfur as the starting materials. The phase, structure, particle morphology and photoluminescence (PL) properties of the as-obtained products were investigated by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM) and photoluminescence spectra. The influence of synthetic time on phase, structure and morphology was systematically investigated and discussed. The possible formation mechanism depending on synthetic time t for the Gd₂O₂S phase has been presented. These results demonstrate that the Gd₂O₂S hollow spheres could be obtained under optimal condition, namely solvothermal temperature T = 220 °C and synthetic time t = 16 h. The as-obtained Gd₂O₂S sample possesses hollow sphere structure, which has a typical size of about 2.5 μm in diameter and about 0.5 μm in shell thickness. PL spectroscopy reveals that the strongest emission peak for the Gd₂O₂S:xTb³⁺ and the Gd₂O₂S:yEu³⁺ samples is located at 545 nm and 628 nm, corresponding to ⁵D₄→⁷F₅ transitions of Tb³⁺ ions and ⁵D₀→⁷F₂ transitions of Eu³⁺ ions, respectively. The quenching concentration of Tb³⁺ ions and Eu³⁺ ions is 7%. In the case of Tb³⁺ and Eu³⁺ co-doped samples, when the concentration of Tb³⁺ or Eu³⁺ ions is 7%, the optimum concentration of Eu³⁺ or Tb³⁺ ions is determined to be 1%. Under 254 nm ultraviolet (UV) light excitation, the Gd₂O₂S:7%Tb³⁺, the Gd₂O₂S:7%Tb³⁺,1%Eu³⁺ and the Gd₂O₂S:7%Eu³⁺ samples give green, yellow and red light emissions, respectively. And the corresponding CIE coordinates vary from (0.3513, 0.5615), (0.4120, 0.4588) to (0.5868, 0.3023), which is also well consistent with their luminous photographs.     

Different crystal structure and photophysical properties of lanthanide complexes with 5-bromonicotinic acid

Five novel lanthanide (Eu³⁺ (1), Tb³⁺ (2), Sm³⁺ (3), Dy³⁺ (4) and Gd³⁺ (5)) complexes with 5-Bromonicotinic acid (5-Brnic) were synthesized and two of them (Tb³⁺, Sm³⁺) were characterized by X-ray diffraction. The results reveal that {[Tb(5-Brnic)₃(H₂O)₃]·H₂O}_n (2) and [Sm(5-Brnic)₃(H₂O)₂·H₂O]₂ (3) exhibit different coordination geometries and crystal structures. Complex 2 has a one-dimensional chain-like polymeric structure through the bridged 5-Brnic anions which links up two neighboring terbium ions, while Complex 3 forms a dimeric molecular structure. The lowest triplet state energy of 5-Brnic was determined to be 24 330 cm⁻¹ corresponded to the 0-0 transition in the phosphorescence spectrum of its gadolinium complex at 411 nm. The strong luminescent emission intensities of these complexes indicated that the triplet state energy of 5-Brnic is suitable for the sensitization of luminescence of Eu³⁺, Tb³⁺, Sm³⁺ and Dy³⁺, especially for that of Tb³⁺ and Dy³⁺.     

The Photophysical Properties of Quaternary Lanthanide (Eu3+, Tb3+, Sm3+, Dy3+) Functional Molecular Complexes

Summary. In this paper, according to the molecular fragment principle, a series of twelve quaternary luminescent lanthanide complex molecular systems were assembled. Both elemental analysis and infrared spectroscopy allowed to determine the complexes formula: Ln(Nic)₃(L)·H₂O, where Ln=Sm, Eu, Tb, Dy; HNic=pyridine-3-carboxylic acid; L=N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), pyrrolidone (pyro). The photophysical properties of these functional molecular systems were studied by recording both ultraviolet-visible absorption, phosphorescence, fluorescence excitation, and emission spectra. It was found that the conjugated pyridine-3-carboxylic acid acts as the main energy donor and luminescence sensitizer due to the suitable energy match and effective energy transfer to the luminescent Ln ³⁺ ions. Amide molecules (DMF, DMA, pyro) were only used as assistant structural ligands to enhance the luminescence. Especially the europium complexes show the strongest luminescence due to the optimum energy transfer between the HNic triplet state energy level and Eu³⁺.     

Three Lanthanide Metal‐Organic Frameworks Based on an Ether‐Decorated Polycarboxylic Acid Linker: Luminescence Modulation,CO2 Capture and Conversion Properties

Three new isostructural 3D lanthanide metal–organic frameworks (Ln‐MOFs), {H[LnL(H₂O)]?2 H₂O}_n ( 1‐Ln ) (Ln=Eu³⁺, Gd³⁺ and Tb³⁺), based on infinite lanthanide‐carboxylate chains were constructed by employing an ether‐separated 5,5′‐oxydiisophthalic acid (H₄L) ligand under solvothermal reaction. 1‐Eu and 1‐Tb exhibit strong red and green emission, respectively, through the antenna effect, as demonstrated through a combination of calculation and experimental results. Moreover, a series of dichromatic doped 1‐Eu_xTb_y MOFs were fabricated by introducing different concentrations of Eu³⁺ and Tb³⁺ ions, and they display an unusual variation of luminescent colors from green, yellow, orange to red. 1‐Eu with channels decorated by ether O atoms and the open metal sites displays good performance for CO₂ capture and conversion between CO₂ and epoxides into cyclic carbonates.     

Synthesis of New LnxBi2–xSe3 (Ln: Sm3+, Eu3+, Gd3+, Tb3+) Nanomaterials and Investigation of Their Optical Properties

New Ln_xBi_2–xSe₃ (Ln: Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺) based nanomaterials were synthesized by a co‐reduction method. Powder XRD patterns indicate that the Ln_xBi_2–xSe₃ crystals (Ln = Sm³⁺, Eu³⁺, x = 0.00–0.44 and Ln = Gd³⁺, Tb³⁺, x = 0.00–0.50) are isostructural with Bi₂Se₃. The cell parameter c decreases for Ln = Eu³⁺, Gd³⁺, Tb³⁺ upon increasing the dopant content (x), while a slightly increases. Changes in lattice parameters could be related to the radii of cations. SEM images show that doping of the lanthanide ions in the lattice of Bi₂Se₃ generally results in nanoflowers. For the terbium compound two kinds of morphologies (nanoflowers and nanobelts) were observed. UV/Vis absorption and emission spectroscopy reveals mainly electronic transitions of the Ln³⁺ ions. Emission spectra show intense transitions from the excited to the ground state of Ln³⁺ and energy transfer from the Bi₂Se₃ lattice. Emission spectra of europium‐doped materials, in addition to the characteristic red emission peaks of Eu³⁺, show an intense blue emission band centered at 432 nm, originating from the 4f⁶5d¹ to 4f⁷ configuration in Eu²⁺. EPR measurements confirm the existence of Eu²⁺ in the materials. Interestingly, for all samples starting at low Ln³⁺ concentration, the emission intensity rises to a maximum at a Ln³⁺ concentration of x = 0.2 and falls again steadily to a minimum at x = 0.45.     

Preparation and luminescent properties of coordination polymers of terbium and europium with 1,4-bis-(4-methoxycarbonyl-3-hydroxyphenoxycarbonyl)butane

Physicochemical properties of new isostructural homo- and heteronuclear coordination polymers of terbium and europium with 1,4-bis-(4-methoxycarbonyl-3-hydroxyphenoxycarbonyl)butane (H₂L) differing in the composition have been studied. The Tb₂L₃·H₂O compound has exhibited efficient sensibilized green luminescence, whereas the corresponding europium-containing polymer EuL₃·H₂O has shown practically no luminescence due to mismatch of energies of the ligand triplet level and the Eu³⁺ ion emitting level. Heteronuclear terbium-europium polymers (Tb_1.5Eu_0.5L₃·H₂O, TbEuL₃·H₂O, and Tb_0.5Eu_1.5L₃·H₂O) show luminescence via the intramolecular transfer of the exiting energy from Tb³⁺ emitting level to Eu³⁺.     

基于吡啶二羧酸配体的稀土配合物的合成、结构及性质

以2,6-二甲基吡啶-3,5-二羧酸（H₂L₁）为主配体,1,10-菲咯啉（L₂）为辅配体,分别与五水合硝酸镝、六水合硝酸铽及六水合硝酸铕通过水热法合成[Dy₂（L₁）₃（L₂）₂]_n（1）、{[Tb₂（L₁）₃（L₂）₂]·5H₂O}_n（2）和{[Eu₂（L₁）₃（L₂）₂]·5H₂O}_n（3）三种配合物。通过单晶X射线衍射、红外光谱、荧光光谱和热重分析对其结构进行了表征与性质研究。结果表明,配合物1~3均以稀土离子为金属节点连接配体L₁^2-和L₂,形成无限延伸的一维链状结构。     

Ten complexes constructed by two reduced Schiff base tetraazamacrocycle ligands: syntheses,structures, magnetic and luminescent properties

Ten new complexes, [Cu₂(L¹)(NO₃)₂]·2H₂O (1), [Cu₄(L¹)₂]·4ClO₄·H₂O (2), [Cu₂(L¹)(H₂O)₂]·(adipate) (3), [Cu₆(L¹)₂(m-bdc)₄]·2DMF·5H₂O (4), [Cu₂(L¹)(Hbtc)]·5H₂O (5), [Cu₂(L¹)(H₂O)₂]·(ntc)·3H₂O (6), [Co₂(L²)]·[Co(MeOH)₄(H₂O)₂] (7), [Co₃(L²)(EtOH)(H₂O)] (8), [Ni₆(L²)₂(H₂O)₄]·H₂O (9) and [Zn₄(L²)(OAc)₂]·0.5H₂O (10), have been synthesized. 1 displays a [Cu₂(L¹)(NO₃)₂] monomolecular structure. 2 shows a supramolecular chain including [Cu₂L¹]²⁺. In 3, two Cu(II) ions are connected by L¹ to form a [Cu₂(L¹)(H₂O)₂]²⁺ cation. In 4, the m-bdc anions bridge Cu(II) ions and L¹ anions to form a layer. Both 5 and 6 display 3-D supramolecular structures. 7 consists of both [Co₂L²]^2? and [Co(MeOH)₄(H₂O)₂]²⁺ units. 8 and 9 show infinite chain structures. In 10, Zn(II) dimers are linked by L² to generate a 3-D framework. The magnetic properties for 4 and 8 and the luminescent property for 10 have been studied.     

Self‐Aggregated Dinuclear Lanthanide(III) Complexes as Potential Bimodal Probes for Magnetic Resonance and Optical Imaging

Homodinuclear lanthanide complexes (Ln=La, Eu, Gd, Tb, Yb and Lu) derived from a bis‐macrocyclic ligand featuring two 2,2′,2′′‐(1,4,7,10‐tetraazacyclododecane‐1,4,7‐triyl)triacetic acid chelating sites linked by a 2,6‐bis(pyrazol‐1‐yl)pyridine spacer (H₂L³) were prepared and characterized. Luminescence lifetime measurements recorded on solutions of the Eu^III and Tb^III complexes indicate the presence of one inner‐sphere water molecule coordinated to each metal ion in these complexes. The overall luminescence quantum yields were determined (?=0.01 for [Eu₂(L³)] and 0.50 for [Tb₂(L³)] in 0.01 M TRIS/HCl, pH 7.4; TRIS=tris(hydroxymethyl)aminomethane), pointing to an effective sensitization of the metal ion by the bispyrazolylpyridyl unit of the ligand, especially with Tb. The nuclear magnetic relaxation dispersion (NMRD) profiles recorded for [Gd₂(L³)] are characteristic of slowly tumbling systems, showing a low‐field plateau and a broad maximum around 30 MHz. This suggests the occurrence of aggregation of the complexes giving rise to slowly rotating species. A similar behavior is observed for the analogous Gd^III complex containing a 4,4′‐dimethyl‐2,2′‐bipyridyl spacer ([Gd₂(L¹)]). The relaxivity of [Gd₂(L³)] recorded at 0.5 T and 298 K (pH 6.9) amounts to 13.7 mM ^?1 s^?1. The formation of aggregates has been confirmed by dynamic light scattering (DLS) experiments, which provided mean particle sizes of 114 and 38 nm for [Gd₂(L¹)] and [Gd₂(L³)], respectively. TEM images of [Gd₂(L³)] indicate the formation of nearly spherical nanosized aggregates with a mean diameter of about 41 nm, together with some nonspherical particles with larger size.     

多色发光层状稀土氢氧化物/聚甲基丙烯酸甲酯复合荧光薄膜的组装

本文通过水热法合成了含有3种不同稀土离子的层状稀土氢氧化物(Gd0.5Tb0.5-xEux)2(OH)5NO3.nH2O,并选择有机物水杨酸(HSA)作为敏化剂,通过在水热条件下的离子交换反应,成功将其以有机阴离子形式与层状稀土氢氧化物插层组装获得有机-无机杂化荧光材料(SA--LRHs∶xEu)。荧光性质测定表明,SA-通过有效的能量转移增强了Tb3+的特征绿色荧光发射,随着Eu3+含量的增加,Eu3+的特征红色荧光发射随之增强,而Tb3+的特征绿色荧光发射随之减弱。在此基础上,将发光颜色可调的有机-无机荧光材料与聚甲基丙烯酸甲酯(PMMA)复合组装出透明的荧光薄膜。     

Tunable luminescence and energy transfer process between Tb3+ and Eu3+ in GYAG:Bi3+, Tb3+, Eu3+ phosphors

A series of Eu³⁺ ions co-doped (Gd_0.9Y_0.1)₃Al₅O₁₂:Bi³⁺, Tb³⁺ (GYAG) phosphors have been synthesized by means of solvothermal reaction method. The XRD pattern of GYAG phosphor sintered at 1500 °C confirms their garnet phase. The luminescence properties of these phosphors have been explored by analyzing their excitation and emission spectra along with their decay curves. The excitation spectra of the GYAG:Bi³⁺, Tb³⁺, Eu³⁺ phosphors consists of broad bands in the shorter wavelength region due to 4f⁸ → 4f⁷5d¹ transition of Tb³⁺ ions overlapped with 6s² → 6s¹6p¹ (¹S₀ → ³P₁) transition of Bi³⁺ ions and the charge transfer band of Eu³⁺–O^2?. The present phosphors exhibit green and red colors due to ⁵D₄ → ⁷F₅ transition of Tb³⁺ ions and ⁵D₀ → ⁷F₁ transition of Eu³⁺ ions, respectively. The emission was shifted from green to red color by co-doping with Eu³⁺ ions, which indicate that the energy transfer probability from Tb³⁺ to Eu³⁺ ions are dependent strongly on the concentration of Eu³⁺ ions.     

Synthesis,spectroscopic, and thermal analyses of trinuclear Mn(II), Co(II), Ni(II), and Zn(II) complexes with some sulfa derivatives

New bi- and trihomonuclear Mn(II), Co(II), Ni(II), and Zn(II) complexes with sulfa-guanidine Schiff bases have been synthesized for potential chemotherapeutic use. The complexes are characterized using elemental and thermal (TGA) analyses, mass spectra (MS), molar conductance, IR, ¹H-NMR, UV-Vis, and electron spin resonance (ESR) spectra as well as magnetic moment measurements. The low molar conductance values denote non-electrolytes. The thermal behavior of these chelates shows that the hydrated complexes lose water of hydration in the first step followed by loss of coordinated water followed immediately by decomposition of the anions and ligands in subsequent steps. IR and ¹H-NMR data reveal that ligands are coordinated to the metal ions by two or three bidentate centers via the enol form of the carbonyl C=O group, enolic sulfonamide S(O)OH, and the nitrogen of azomethine. The UV-Vis and ESR spectra as well as magnetic moment data reveal that formation of octahedral [Mn₂L¹(AcO)₂(H₂O)₆] (1), [Co₂(L¹)₂(H₂O)₈] (2), [Ni₂L¹(AcO)₂(H₂O)₆] (3), [Mn₃L²(AcO)₃(H₂O)₉] (5), [Co₃L²(AcO)₃(H₂O)₉] · 4H₂O (6), [Ni₃L²(AcO)₃(H₂O)₉] · 7H₂O (7), [Mn₃L³(AcO)₃(H₂O)₆] (9), [Co₂(HL³)₂(H₂O)₈] · 4H₂O (10), [Ni₃L³(AcO)₃(H₂O)₉] (11), [Mn₃L⁴(AcO)₃(H₂O)₉] · H₂O (13), [Co₂(HL⁴)₂(H₂O)₈] · 5H₂O (14), and [Ni₃L⁴(AcO)₃(H₂O)₉] (15) while [Zn₂L¹(AcO)₂(H₂O)₂] (4), [Zn₃L²(AcO)₃(H₂O)₃] · 2H₂O (8), [Zn₃L³(AcO)₃(H₂O)₃] · 3H₂O (12), and [Zn₃L⁴(AcO)₃(H₂O)₃] · 2H₂O (16) are tetrahedral. The electron spray ionization (ESI) MS of the complexes showed isotope ion peaks of [M]⁺ and fragments supporting the formulation.     

Synthesis,characterization, thermal,and antimicrobial studies of binuclear metal complexes of sulfa-guanidine Schiff bases

A series of metal complexes of Schiff bases derived from condensation of sulfa-guanidine with 1-benzoylacetone (H₂L¹), 2-hydroxybenzophenol (H₂L²), dibenzoylmethane (H₂L³), 5-methylisatine (H₂L⁴), and 1-methylisatine (H₂L⁵) have been synthesized. The complexes are characterized by elemental analysis, molar conductance, magnetic moment measurements, IR, UV–Vis, ¹H NMR, and ESR spectra, as well as thermogravimetric analysis. The low molar conductance values indicate the complexes are nonelectrolytes. IR and ¹H NMR spectra show that H₂L¹–H₂L⁵ are coordinated to metal ions by two bidentate centers. Mn(II), Co(II), Ni(II), and Cu(II) complexes display paramagnetic behavior, whereas the Zn(II)-complex was diamagnetic. All studies confirm the formation of an octahedral geometry for [Cu₂L¹(AcO)₂(H₂O)₆] · 3H₂O (1), [Mn₂L⁴(AcO)₂(H₂O)₆] · 2H₂O (6), [Ni₂L⁴(AcO)₂(H₂O)₆] · 2H₂O (8), a tetrahedral geometry for [Cu₂L²(AcO)₂(H₂O)₂] (2), [Cu₂(L⁴)₂] (4), [Co₂(L⁴)₂] · 2H₂O (7) and [ZnHL⁴(AcO)(H₂O)] · 2H₂O (9) and a trigonal bipyramid geometry for [Cu₂L³(AcO)₂(H₂O)₄] (3) and [Cu₂HL⁵(AcO)₃(H₂O)₃] · H₂O (5). H₂L⁴ was most effective on Gram negative, Gram positive bacteria, and fungi (diameters inhibition zone ranged between 10.5–27.5 mm) after 24 and 48 h, respectively. Complex 8 showed moderate antimicrobial activity. Its minimum inhibitory concentration (MIC) against Escherichia coli, Bacillus subtilis, Candida albicans and Aspargllus flavas was 20 mg L^–1. The compound proved to be of moderate toxicity and its LD₅₀ was 20 mg L^–1.     

Luminescence in NaLn(SO4)2H2O: A host lattice with high-energy vibrations

The luminescence of Ce³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺, and Dy³⁺ in NaLn(SO₄)₂H₂O (Ln = lanthanide) is reported. Only Ce³⁺, Gd³⁺, and Tb³⁺ show efficient emission. This is explained in terms of an energy-gap law. Energy transfer is studied in several codoped compositions. The mutual transfer between Gd³⁺ ions is the only one encountered with high probability. The several transfers are discussed and where possible their rates are calculated.     

Trigonal (-3) symmetry octahedral lanthanide(III) complexes of zwitterionic tripodal ligands: luminescence and magnetism

Sandwich coordination complexes, [Ln^III(H₃L)₂]X₃?solvents, of Tb(III), Eu(III), Dy(III), Ho(III) and Er(III) were prepared with two new zwitterionic ester-substituted tripodal amine ligands, tris((2-hydroxy-5-n-butyl benzoate)aminoethyl)-amine (H₃L¹) and tris((2-hydroxy-5-methyl benzoate)aminoethyl)-amine (H₃L²). These ligands were synthesised by condensation of the appropriately substituted salicylaldehyde with tris(2-aminoethyl)amine (tren) followed by in situ reduction of the tris-imine to tris-amine. Subsequent 2:1 reaction with lanthanide(III) ions yields [Ln^III(H₃L)₂]X₃?solvents (L = L¹, L²; X = Cl^?, NO₃^?; solvents = MeOH or H₂O). All complexes were characterised by microanalysis, infrared spectroscopy, high resolution mass spectrometry and solid-state photoluminescence measurements. The crystal structures of [Tb^III(H₃L¹)₂]Cl₃·6MeOH, [Dy(H₃L¹)₂]Cl₃·6MeOH, [Eu^III(H₃L¹)₂]Cl₃·6MeOH and [Tb^III(H₃L¹)₂](NO₃)₃ reveal high-crystallographic ?3 symmetry at the O₆-coordinated octahedral lanthanide(III) ions and that the tripodal ligands are bound in zwitterionic form: the protons from the phenolic oxygens have migrated to the amino nitrogens. Photoluminescence measurements indicate various degrees of energy transfer of the ligand chromophore to the lanthanide ions, as both ligand and lanthanide emission features are observed. Despite the high-crystallographic symmetry and the likely small transverse magnetic anisotropy of the complexes, no evidence of slow relaxation of the magnetisation, characteristic of a single-molecule magnet, was observed for [Tb^III(H₃L¹)₂]Cl₃·MeOH·3H₂O, [Dy^III(H₃L¹)₂]Cl₃·6H₂O, [Ho^III(H₃L¹)₂](NO₃)₃·2H₂O, [Er^III(H₃L¹)₂]·H₂O and [Tb^III(H₃L¹)₂](NO₃)₃ down to 2.0 K.     

多色发光层状稀土氢氧化物/聚甲基丙烯酸甲酯复合荧光薄膜的组装

本文通过水热法合成了含有3种不同稀土离子的层状稀土氢氧化物 (Gd_0.5Tb_0.5-xEu_x)₂(OH)₅NO₃·nH₂O, 并选择有机物水杨酸(HSA)作为敏化剂, 通过在水热条件下的离子交换反应, 成功将其以有机阴离子形式与层状稀土氢氧化物插层组装获得有机-无机杂化荧光材料(SA^--LRHs:xEu)。荧光性质测定表明, SA^-通过有效的能量转移增强了Tb³⁺的特征绿色荧光发射, 随着Eu³⁺含量的增加, Eu³⁺的特征红色荧光发射随之增强, 而Tb³⁺的特征绿色荧光发射随之减弱。在此基础上, 将发光颜色可调的有机-无机荧光材料与聚甲基丙烯酸甲酯(PMMA)复合组装出透明的荧光薄膜。     

A new disordered langbeinite‐type compound,K2Tb1.5Ta0.5P3O12, and Eu3+‐doped multicolour light‐emitting properties

For the first time, a new langbeinite‐type phosphate, namely potassium terbium tantalum tris(phosphate), K₂Tb_1.5Ta_0.5(PO₄)₃, has been prepared successfully using a high‐temperature flux method and has been structurally characterized by single‐crystal X‐ray diffraction. The results show that its structure can be described as a three‐dimensional open framework of [Tb_1.5Ta_0.5(PO₄)₃]_∞ interconnected by K⁺ ions. The Tb^III and Ta^V cations in the structure are disordered and occupy the same crystallographic sites. The IR spectrum, the UV–Vis spectrum, the morphology and the Eu³⁺‐activated photoluminescence spectroscopic properties were studied. A series of Eu³⁺‐doped phosphors, i.e. K₂Tb_1.5–xTa_0.5(PO₄)₃:xEu³⁺ (x = 0.01, 0.03, 0.05, 0.07, 0.10), were prepared via a solid‐state reaction and the photoluminescence properties were studied. The results show that under near‐UV excitation, the luminescence colour can be tuned from green through yellow to red by simply adjusting the Eu³⁺ concentration from 0 to 0.1, because of the efficient Tb³⁺→Eu³⁺ energy‐transfer mechanism.     

Excited State Properties of Lanthanide(III) Complexes with a Nonadentate Bispidine Ligand

Eu^III, Tb^III, Gd^III and Yb^III complexes of the nonadentate bispidine derivative L² (bispidine=3,7-diazabicyclo[3.3.1]nonane) were successfully synthesized and their emission properties studied. The X-ray crystallography reveals full encapsulation by the nonadentate ligand L² that enforces to all Ln^III cations a common highly symmetrical capped square antiprismatic (CSAPR) coordination geometry (pseudo C_4v symmetry). The well-resolved identical emission spectra in solid state and in solution confirm equal structures in both media. As therefore expected, this results in long-lived excited states and high emission quantum yields ([Eu^IIIL²]⁺, H₂O, 298 K, τ=1.51 ms, ϕ=0.35; [Tb^IIIL²]⁺, H₂O, 298 K, τ=1.95 ms, ϕ=0.68). Together with the very high kinetic and thermodynamic stabilities, these complexes are a possible basis for interesting biological probes.     

A Highly Stable Yttrium Organic Framework as a Host for Optical Thermometry and D2O Detection

The yttrium organic framework (Y_0.89Tb_0.10Eu_0.01)₆(BDC)₇(OH)₄(H₂O)₄ (BDC=benzene-1,4-dicarboxylate) is hydrothermally stable up to at least 513 K and thermally stable in air in excess of 673 K. The relative intensities of luminescence of Tb³⁺ and Eu³⁺ are governed by Tb³⁺-to-Eu³⁺ phonon-assisted energy transfer and Tb³⁺-to-ligand back transfer and are responsible for the differing temperature-dependent luminescence of the two ions. This provides a ratiometric luminescent thermometer in the 288–573 K temperature range, not previously seen for MOF materials, with a high sensitivity, 1.69±0.04 % K⁻¹ at 523 K. In aqueous conditions, loosely bound H₂O can be replaced by D₂O in the same material, which modifies decay lifetimes to yield a quantitative luminescent D₂O sensor with a useful sensitivity for practical application.