The phenomenon of fluorescence enhancement for the system of terbium(b!) with terephthalic acid (benzene-1,4-dicarboxylic acid (TPA)) in the presence of an excess of La3+ in Triton X-100 aqueous solution has been stud...The phenomenon of fluorescence enhancement for the system of terbium(b!) with terephthalic acid (benzene-1,4-dicarboxylic acid (TPA)) in the presence of an excess of La3+ in Triton X-100 aqueous solution has been studied. The fluorescence intensity of Tbb!-TPA system can be greatly increased by La3+. The intermolecular transfer of energy was responsible for the mechanism of the fluorescence enhancement. Triton X-100 plays an important role for the stabilization of the system. The system, having the maximum excitation and emission wavelengths at 256 nm and 546 nm, respectively, shows a constant fluorescence intensity over the pH range between 4-6. The fluorescence intensity is a linear function of Tb3+concentration in the range of 1.00 ?展开更多
The formation behaviors of terbium sesquisulfide(Tb_2S_3)and holmium sesquisulfide(Ho_2S_3)synthesized via the sulfurization of their oxide powders using CS_2 gas in the range of temperature 673 to 1323 K were investi...The formation behaviors of terbium sesquisulfide(Tb_2S_3)and holmium sesquisulfide(Ho_2S_3)synthesized via the sulfurization of their oxide powders using CS_2 gas in the range of temperature 673 to 1323 K were investigated. In the sulfurization of Tb_4O_7 powder, Tb_2O_3 and Tb_2O_2S were formed in the initial stage of reaction, and α-Tb_2S_3 was finally formed at higher temperature. For long sulfurization time of 8 h, single-phase α-Tb_2S_3 could be synthesized at 1323 K. In the sulfurization of Ho_2O_3 powder using CS_2 gas, only Ho_2O_2S was formed as an intermediate product. At a sulfurization temperature above 873 K, Ho_2O_2S was formed in the initial stage of reaction, and single-phase δ-Ho_2S_3 was formed at 1323 K for 8 h instead of Ho_2O_2S. Furthermore, the influence of the addition of carbon black to the sulfurization of Ho_2O_3 powder using CS_2 gas was investigated, and the result implied that the reactions were accelerated slightly by the addition of carbon black.展开更多
Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indic...Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indicate that the complexes have the composition of Eu(phen)L3·1/2H2O, Eu0.5RE0.5(phen)L3·1/2H2O; Tb(phen)L3·H2O and Tb0.5RE0.5(Phen)L3·1/2H2O. (RE=Y3+, La3+ and Gd3+; L=biphenyl 4-carboxylic acid; phen=o-Phenanthroline). The studies of their IR, UV 1H NMR and molar conductivities demonstrate that biphenyl 4-carboylic acid is bounded with RE(Ⅲ) ion. Rare earth ions coordinate with two nitrogen atoms of phen molecules directly in these rare earth complexes. The fluorescence spectra and fluorescence lifetimes of the rare earth complexes show that the fluorescent intensity and lifetime of a series of europium complexes are longer than those of the series of terbium complexes as having the some ligands. There are better fluorescent intensity and lifetime of hetero-nuclear rare earth complexes than homo-nuclear rare earth complexes for europium complexes. The fluorescence emission intensity of Eu3+ is raised by inert fluorescent rare earth ions (Y3+, Gd3+ and La3+), but in Tb3+ hetero-nuclear rare earth complexes the intensity of Tb3+ ions are quenched by the inert fluorescent rare earth ions.展开更多
The fluorescence of terbium (Ⅲ) was enhanced by about three orders of magnitude in the presence of trimellitic acid (benzene-1, 2, 4-tricarboxylic acid (TLA)) in aqueous solution at pH 6. The fluorescence inten...The fluorescence of terbium (Ⅲ) was enhanced by about three orders of magnitude in the presence of trimellitic acid (benzene-1, 2, 4-tricarboxylic acid (TLA)) in aqueous solution at pH 6. The fluorescence intensity could be greatly increased when the system of Tb^3+-TLA was treated with La^3+ (or Gd^3+) and TritonX- 100. The addition of La^3+ (or Gd^3+) enhanees the fluorescence of the system by about two orders of magnitude due to cofluorescenee, and the TritonX-100 micellar medium plays an important role for stabilization of the system. Both the intermolecular energy transfer mode and intramolecular energy transfer mode are responsible for the mechanism of fluorescence enhancement. In the optimum condi- tions, the fluorescence intensity is a linear function of Tb3~ concentration in the range of 7.8 × 10^-9-3.6 × 10^4 mol/L for the system Tb^3+-La^3+-TLA and 1.0 × 10^-8-4.7 × 10^-5 mol/L for the system Tb^3+-Gd^3+-TLA, and the limits of detection are 4.6 × 10^-10 mol/L and 6.0 × 10^-10 mol/L, respectively.展开更多
A terbium benzoate complex with 1,10-phenanthroline [Tb(ba)3(phen)]2, where ba = benzoate and phen = 1,10-phenanthroline, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in tri...A terbium benzoate complex with 1,10-phenanthroline [Tb(ba)3(phen)]2, where ba = benzoate and phen = 1,10-phenanthroline, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.7881(5), b = 11.9262(6), c = 12.4249(6) ?, a = 105.1260(10), β = 93.6010(10), ? = 113.3350(10)o, (C33H23N2O6Tb)2, Mr = 1404.90, V = 1391.87(12) ?3, Z = 1, Dc = 1.676 g/cm3, μ(MoKα) = 2.590 mm-1, F(000) = 696, the final R = 0.0277 and wR = 0.0670 for 6085 observed reflections with I > 2σ(I). The crystal consists of binuclear molecules of the title compound. Each Tb3+ ion is nine-coordinated to one 1,10-phenan- throline molecule, one bidentate carboxylate group and four bridging carboxylate groups. The carboxylate groups are bonded to the terbium ion in three modes: the chelating bidentate, bridging bidentate and bridging-chelating tridentates. Excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The results of thermal analysis indicate that the complex [Tb(ba)3phen]2 is very thermal stable.展开更多
A terbium o-methylbenzoate complex with 1,10-phenanthroline, Tb(o-MBA)_3phen(where o-MBA = o-methylbenzoate and phen = 1,10-phenanthroline) was prepared from ethanol solutionand its crystal structure was determined by...A terbium o-methylbenzoate complex with 1,10-phenanthroline, Tb(o-MBA)_3phen(where o-MBA = o-methylbenzoate and phen = 1,10-phenanthroline) was prepared from ethanol solutionand its crystal structure was determined by X-ray diffraction. The crystal of the complexTb(o-MBA)_3phen belongs to triclinic crystal system and P1 (#2) space group. The crystal data are asfollows: a = 1.4371(4) nm, b = 1.7387(2) nm, c = 1.3109(2) nm, α = 96.37(1)°, β = 107.21(2)°,γ= 82.78(2)°, Ⅴ= 3.094(1) nm^3, Z= 2, M_r = 1489.12, D_c= 1.598 g·cm^(-3), μ = 2.330 mm^(-1)and F(000) = 1488.00. The final R and R_w are 0.038 and 0.047 for 8668 [Ⅰ > 2σ(Ⅰ)] uniquereflections, respectively. In the complex each Tb^(3+) ion is eight-coordinated by one1,10-phenanthroline molecule, one bidentate carboxylate group and four bridging carboxylate groups.The carboxylate groups are bonded to the terbium ion in two modes: the chelating bidentate and thebridging bidentate. Excitation and luminescence data observed at room temperature show that thetitle complex emits strong green fluorescence under ultraviolet light. The results of thermalanalysis indicate that the complex Tb(o-MBA)_3phen is quite stable to heat.展开更多
The binding of Tb 3+ to chicken apoovotransferrin was studied by monitoring the fluorescent intensity of Tb 3+ at 549 nm. The conditional equilibrium constants for the complexation of Tb 3+ by chicken apoovotransferri...The binding of Tb 3+ to chicken apoovotransferrin was studied by monitoring the fluorescent intensity of Tb 3+ at 549 nm. The conditional equilibrium constants for the complexation of Tb 3+ by chicken apoovotransferrin in 0 1 mol/L hepes, at pH 7 4 and room temperature were measured. The successive macroscopic binding constants are lg K 1=9 08±0 12 and lg K 2=7 36±0 22. The molar fluorescence enhancement of Tb 3+ apoovotransferrin complex is (2 06±0 14)×10 4 mol -1 ·L. The fluorescence quenching experiment and the titration of N terminal monoferric ovotransferrin showed that Tb 3+ has a preference for being bound to the N terminal binding site of apoovotransferrin.展开更多
The phenomenon of fluorescence enhancement for the system of terbium( Ⅲ ) with trimesic acid [ ben-zene-1, 3, 5-tricarboxylic acid (TMA)] in the presence of an excase of La ̄(3+) in gelatin aqusous solution wasstudi...The phenomenon of fluorescence enhancement for the system of terbium( Ⅲ ) with trimesic acid [ ben-zene-1, 3, 5-tricarboxylic acid (TMA)] in the presence of an excase of La ̄(3+) in gelatin aqusous solution wasstudied. The fluorescence intensity of Tb ̄Ⅲ -TMA system can be greatly increased by La ̄(3+) , which causedthe largest enhancement of the fluorescence intensity over two orders of magnitude. The intermolecular transfer of energy was responsible for the mechanism of the fluorascence enhancement. Gelatin plays animportant role for the stabilization of the system. The system, having the maximum excitation and emis-sion wavelengths at 260 nm and 549 nm, respectively, shows a constant fluorescence interisity over the pHrange 4~6. The fluorescence intensity is a linear function of Tb ̄(3+) concentration in the range of 8. 0 ×10  ̄(-9)~ 2. 6 × 10 ̄(-7) mol· L ̄(-1) and the limit of detection is 2.0 × 10 ̄(-9) mol·L ̄(-1) . The optimized procedurewas used for the determination of trace amount of terbium in rare earth oxides and international standardreference rocks with satisfactory results.展开更多
Poly (N-vinylacetatnide) ( PNVA) was synthesized by free radical polymerization in ethanol solution, in which alpha, alpha'-azobisisobutyronitrile was used as an initiator. Tb(III)-PNVA polymer was prepared and ch...Poly (N-vinylacetatnide) ( PNVA) was synthesized by free radical polymerization in ethanol solution, in which alpha, alpha'-azobisisobutyronitrile was used as an initiator. Tb(III)-PNVA polymer was prepared and characterized by ultraviolet-visual (UV), fourier transform infrared (FIF-IR), X-ray photoelectron spectroscopy (XPS) and fluorescence spectroscopy. The experimental results of UV, FT-IR and XPS show that the Tb (III)-PNVA electrovalent complex is formed by electrostatic interaction between terbium (III) cation and complexible atoms of acylamino group in the pendant chain of the polymer. The fluorescence spectrum of the complex exhibits intensive characteristic emission of terbium at 490, 545 and 584 run, which are assigned to D-5(4)->F-7(6), D-5(6)->F-5(6) and D-5(4)->F-7(3) transition, indicating that there exists an efficient intermolecular energy transfer from the polymer ligand to the central rare earth ion. The emission intensity of the complex is increased with the increasing concentration of Tb (III) ion until the weight ratio of Tb (III) on to PNVA is 1.5% (mass fraction), and decreased with the further increasing concentration of Tb (III) ion, which is a typical concentration quenching behavior.展开更多
A novel terbium-mercury complex [Tb(IA)3(H3 O)2]2 n(2 n HgCl4)(n Hg2 Cl5)·n H3 O· 3 n H2 O(1, HIA = isonicotinic acid) has been synthesized through hydrothermal reactions and characterized by single-crystal ...A novel terbium-mercury complex [Tb(IA)3(H3 O)2]2 n(2 n HgCl4)(n Hg2 Cl5)·n H3 O· 3 n H2 O(1, HIA = isonicotinic acid) has been synthesized through hydrothermal reactions and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the C2/c space group of monoclinic system with a = 24.2347(5), b = 20.8342(6), c = 15.3206(3) ?, β = 128.257(2)°, V = 6074.3(2) ?3, C36H41Cl13Hg4N6O20Tb2, Mr = 2458.80, Z = 4, Dc = 2.689 g/cm3, μ(Mo Kα) = 13.014 mm–1 and F(000) = 4520. The crystal structure of 1 is characterized by a one-dimensional(1-D) chain-like structure. Solid-state UV/Vis diffuse reflectance spectrum reveals the existence of a wide optical band gap of 3.36 eV. Solid-state photoluminescence experiment uncovers that it shows reddish brown upconversion emission. The emission bands are originated from the characteristic emission of the 4 f electrons intrashell transition of the 5D4 → 7 FJ(J = 6, 5, 4) of the Tb3+ ions. Energy transfer mechanism is explained by the energy level diagram of the Tb3+ ion and the isonicotinic acid ligand. It shows a remarkable CIE chromaticity coordinates(0.4158, 0.4005).展开更多
To understand the nature and behavior of rare earth metals in their liquid phases, accurate values of their physical properties are essential. However, to measure their physical properties, the samples should be maint...To understand the nature and behavior of rare earth metals in their liquid phases, accurate values of their physical properties are essential. However, to measure their physical properties, the samples should be maintained in liquid phases for prolonged time, and this raises a formidable challenge. This is mainly explained by their high melting temperatures (e.g., 1629 K for Tb), high vapor pressure, and the risk of melt contamination with a crucible or support. An electrostatic levitation furnace alleviated these difficulties and allowed the determination of density, surface tension, and viscosity of several metals above their melting temperature. Here, first, the levitation furnace facility and the noncontact diagnostic procedures were briefly discussed, followed by the explanation of their thermophysical property measurements over wide temperature ranges. The density was obtained using an ultraviolet-based imaging technique that allowed excellent illumination, even at elevated temperatures. Over the 1615 to 1880 K temperature span, the density measurements could be expressed as p(T) =7.84 × 10^3 -0.47 (T - Tm) (kg · m^-3) with Tm = 1629 K, yielding a volume expansion coefficient a(T) = 6.0 × 10^-5 (K^-1). In addition, the surface tension and the viscosity could be determined by inducing a drop oscillation to a molten sample. Using this technique, the surface tension data could be expressed as σ(T) = 8.93 × 10^2 - 0.10 (T - Tm)(mN· m^-1) and those for viscosity as η(T) =0.583 exp [4.1 × 10^4/(RT)] (MPa·s) over the 1690 to 1980 K temperature range展开更多
Three new complexes TbL3dipy (H2O)2, TbL3phen (H2O) 2 and TbL2 (TPPO) 2NO3 were synthesized (L = phenylglyoxylate ion, dipy = 2, 2-dipyridine, phen = 1,10-phenanthmline, TPPO = Triphenyl phosphine oxide). Elem...Three new complexes TbL3dipy (H2O)2, TbL3phen (H2O) 2 and TbL2 (TPPO) 2NO3 were synthesized (L = phenylglyoxylate ion, dipy = 2, 2-dipyridine, phen = 1,10-phenanthmline, TPPO = Triphenyl phosphine oxide). Elemental analysis, conductivity, IR spectra, and ^1HNMR spectra studies were performed. IR spectra indicate that the carboxylate ion of phenylglyoxylate is coordinated to the Tb(Ⅲ) ion as an unidentate ligand. In ^1HNMR, the signals of different hydrogens in phenylglyoxylate ion shift upfield. The excitation and emission spectra of the three solid complexes were recorded at morn temperature, in which the optimum excitation wavelengths are, 361.0, 359.0 and 367.0 nm for these three complexes, respectively. Four emission bands due to the ^5D4-^7Fj(j = 6, 5, 4, 3) transitions were observed for TbL3dipy(H2O)2(489.0, 545.0, 584.0, 620.0 nm) and TbL3phen(H2O)2(490.0, 544.0, 583.0, 620.0 nm). Under the same conditions, only one emission band due to the ^5D4-^7F5 transition was observed for the complex TbL2(TPPO)2NO3. The emission intensity of TbL3dipy(H2O)2 is the strongest among the three complexes.展开更多
A dual functional coordination polymer, namely, {[Tb(mat)(1.5)H2O]·2.5H2O}n(1, H2mta = 2-methoxyterephthalic acid), was synthesized under solvothermal condition and characterized by single-crystal X-ray dif...A dual functional coordination polymer, namely, {[Tb(mat)(1.5)H2O]·2.5H2O}n(1, H2mta = 2-methoxyterephthalic acid), was synthesized under solvothermal condition and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, X-ray powder diffraction analysis(PXRD), and thermogravimetric analysis(TGA). Complex 1 exhibits a 3D framework based on infinite rod-shaped secondary building units(SBUs). Furthermore, the solid-state luminescent property and magnetic properties of the complex were investigated at room temperature; the results show that the complex exhibits excellent luminescent properties in green luminescence and weak antiferromagentic behavior.展开更多
Ethyl methacrylate (EMA) doped with luminescent ternary terbium complex (Tb(acac) 3·dam) with acetylacetone (Hacac) and diantipylmethane (dam) was incorporated into the microporous silica gel. With the polymeriz...Ethyl methacrylate (EMA) doped with luminescent ternary terbium complex (Tb(acac) 3·dam) with acetylacetone (Hacac) and diantipylmethane (dam) was incorporated into the microporous silica gel. With the polymerization of EMA, the hybrid material containing Tb(acac) 3·dam was obtained. The hybrid material exhibited good toughness and transparency and higher thermal stability than that of the pure complex and pure polymer matrix. In the range of doping concentration of Tb(acac) 3·dam (0.05%, 0.1%, 0.2%, 0.5%, 1.0%, 2.0% and 5.0%), emission intensity increases with the increasing of corresponding doping concentration and concentration quenching effect has not taken place.展开更多
A novel Tb(Ⅲ) coordination polymer [Tb(bpapO2)2(NO3)3]n [bpapO2 = N2,N6- bi(pyridin-2-yl)pyridine-2,6-diamine-N,N'-dioxide-dioxide] has been synthesized and it exhibits terbium’s characteristic fluorescent ...A novel Tb(Ⅲ) coordination polymer [Tb(bpapO2)2(NO3)3]n [bpapO2 = N2,N6- bi(pyridin-2-yl)pyridine-2,6-diamine-N,N'-dioxide-dioxide] has been synthesized and it exhibits terbium’s characteristic fluorescent emission under UV radiation of 326 nm at room temperature. X-ray structural determination indicates that each terbium(Ⅲ) ion, centered in TbO8 core, connects to three adjacent coordinate centers via a bi-dentate ligand bpapO2, forming a one-dimensional coordination polymer. The compound crystallizes in the triclinic system, space group P1, with a = 11.2271(5), b = 11.7997(5), c = 14.8016(6) Ⅲ, α = 72.7060(10), β = 89.9630(10), γ = 66.7680(10)o, Z = 2, Dc = 1.822 g/cm3, V = 1705.14(13) Ⅲ3, F(000) = 932, the final R = 0.0340 and wR = 0.0669 for 4812 observed reflections with I 2σ(I).展开更多
This article describes a new method for the simultaneous determination of trace rare earth elements (REEs) and non rare earth elements (NREEs) in high purity terbium oxide by ICP-AES after HPLC separation using P507 r...This article describes a new method for the simultaneous determination of trace rare earth elements (REEs) and non rare earth elements (NREEs) in high purity terbium oxide by ICP-AES after HPLC separation using P507 resin. The chromatographic separation of the analytes from the matrix using dilute nitric acid as mobile phase was studied. The experimental results showed that a favorable separation of trace metals (Cu and Gd) from the matrix (Tb) can easily be achieved by elution with dilute nitric acid within 25 min. The proposed method was applied to the determination of trace metals (Ca, Cu, Mg, Mn, Ni, Si, La, Ce, Pr, Nd, Sm, Eu and Gd) in high purity terbium oxide. The detection limits (DLs) for the analytes ranged from 0.4-4.0 μg\5g -1, and the recoveries are from 78%-105%.展开更多
A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid(H4bptc) has been synthesized, {[Tb(Hbptc)(H2O)4]×H2O}n(1). Its structure was determined by single-crystal X-ray diffraction analysis and fu...A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid(H4bptc) has been synthesized, {[Tb(Hbptc)(H2O)4]×H2O}n(1). Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. Title complex crystallizes in monoclinic, space group P21/n with a = 14.090(2), b = 8.0824(13), c = 15.5591(17) A, V = 1775.4(5) A3, Mr = 576.22, Dc = 2.156 g/cm3, μ(Mo Kα) = 4.059 mm-1, F(000) = 1128, Z = 4, the final R = 0.027 and w R = 0.0726 for 3296 observed reflections(I > 2σ(I)). Complex 1 exhibits a 2 D layer structure, and such layers are further united together into a three-dimensional supramolecular structure through π···π interaction and intricate hydrogen bonding. The fluorescence excitation and emission spectroscopy of 1 showed that H4 bptc is a kind of highly efficient sensitizer for terbium(Ⅲ) ion. The title complex also displays efficient ligand sensitized luminescence in the visible region with long lifetime of 2.02 ms in the solid state.展开更多
A new coordination compound with formula [Tb(2-TC)3(DMF)]n (1, 2-TC = 2-thio- phenecarboxylic ligand and DMF = dimethylformamide) was synthesized by solvothermal method. The structure of compound 1 was determine...A new coordination compound with formula [Tb(2-TC)3(DMF)]n (1, 2-TC = 2-thio- phenecarboxylic ligand and DMF = dimethylformamide) was synthesized by solvothermal method. The structure of compound 1 was determined by single-crystal X-ray diffraction analyses, and characterized by elemental analyses, IR and powder X-ray diffraction. Structure analysis reveals compound 1, exhibiting a one-dimensional chain structure, crystallizes in triclinic space group P21/c, with a = 9.2751(19), b = 16.490(3), c = 15.865(5) A, β = 118.98(2)°, V= 2122.7(9)A3, D,. = 1.916 g/cm3, Mr= 612.45 (C18H15NO7S3Tb), F(000) = 1196,μ(MoKa) = 3.67 mm-1, Z = 4, R = 0.0616 and wR = 0.0962 for 3865 observed reflections (I 〉 2o(I)), and R = 0.1092 for all data. Meanwhile, the photoluminescent properties of compound 1 were also investigated in the solid state at room temperature.展开更多
Tb(Ⅲ )-trimesic acid (TMA) luminescent complexes were synthesized in the polyvinylpyrrolidone (PVP) matrix. The elemental analysis, inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and fourie...Tb(Ⅲ )-trimesic acid (TMA) luminescent complexes were synthesized in the polyvinylpyrrolidone (PVP) matrix. The elemental analysis, inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and fourier-transform infrared spectroscopy (FT-IR) indicated that its chemical constitution is PVP/Tb(MTA)· 4H2O. The XRD patterns showed that the complex is a new kind of crystal. The TEM image indicates that the complex is rod shaped. The rod diameter is about 200 nm, and the length ranges from hundred of nanometer to a few micrometers. In addition, the dispersity is better. TG-DTA curves indicate that the complex is thermally stable before 463℃. Photoluminescence analysis indicates that the complex emits Tb^3+ characteristic luminescence under ultraviolet excitation.展开更多
A new terbium(Ⅲ) complex Tb(C20H14O3N)3(C12H8N2)(H2O)·H2O has been synthesized with 2-diphenylanine carbonyl benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: triclini...A new terbium(Ⅲ) complex Tb(C20H14O3N)3(C12H8N2)(H2O)·H2O has been synthesized with 2-diphenylanine carbonyl benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: triclinic, space group P1, a =11.6034(6), b = 16.2465(8), c = 16.4427(8) A, α = 73.168(5)°, β = 88.655(4)°, γ = 82.865(4)°, V = 2943.7(3)A^3, Dc = 1.494 g/cm^3, Z = 2, μ(MoK α) = 1.272 mm^-1, F(000) = 1348, the final R = 0.0535 and wR = 0.0809. The Tb(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry. The complex shows four fluorescence emission bands arising from the transitions of Tb^3+: 5D4 → 7F6(491 nm), 5D4 → 7F5(546 nm), 5D4 → 7F4(585 nm) and 5D4→7F3(621 nm). Also reported are the magnetic and thermal stability properties of the complex.展开更多
基金This project is financially supported by the Gansu Province Natural Science Foundation (ZR-97-21)
文摘The phenomenon of fluorescence enhancement for the system of terbium(b!) with terephthalic acid (benzene-1,4-dicarboxylic acid (TPA)) in the presence of an excess of La3+ in Triton X-100 aqueous solution has been studied. The fluorescence intensity of Tbb!-TPA system can be greatly increased by La3+. The intermolecular transfer of energy was responsible for the mechanism of the fluorescence enhancement. Triton X-100 plays an important role for the stabilization of the system. The system, having the maximum excitation and emission wavelengths at 256 nm and 546 nm, respectively, shows a constant fluorescence intensity over the pH range between 4-6. The fluorescence intensity is a linear function of Tb3+concentration in the range of 1.00 ?
文摘The formation behaviors of terbium sesquisulfide(Tb_2S_3)and holmium sesquisulfide(Ho_2S_3)synthesized via the sulfurization of their oxide powders using CS_2 gas in the range of temperature 673 to 1323 K were investigated. In the sulfurization of Tb_4O_7 powder, Tb_2O_3 and Tb_2O_2S were formed in the initial stage of reaction, and α-Tb_2S_3 was finally formed at higher temperature. For long sulfurization time of 8 h, single-phase α-Tb_2S_3 could be synthesized at 1323 K. In the sulfurization of Ho_2O_3 powder using CS_2 gas, only Ho_2O_2S was formed as an intermediate product. At a sulfurization temperature above 873 K, Ho_2O_2S was formed in the initial stage of reaction, and single-phase δ-Ho_2S_3 was formed at 1323 K for 8 h instead of Ho_2O_2S. Furthermore, the influence of the addition of carbon black to the sulfurization of Ho_2O_3 powder using CS_2 gas was investigated, and the result implied that the reactions were accelerated slightly by the addition of carbon black.
基金Project supported by the National Natural Science Foundation of China (20461002)Chunhui Plan of MOE (Z2004-2-15029)
文摘Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indicate that the complexes have the composition of Eu(phen)L3·1/2H2O, Eu0.5RE0.5(phen)L3·1/2H2O; Tb(phen)L3·H2O and Tb0.5RE0.5(Phen)L3·1/2H2O. (RE=Y3+, La3+ and Gd3+; L=biphenyl 4-carboxylic acid; phen=o-Phenanthroline). The studies of their IR, UV 1H NMR and molar conductivities demonstrate that biphenyl 4-carboylic acid is bounded with RE(Ⅲ) ion. Rare earth ions coordinate with two nitrogen atoms of phen molecules directly in these rare earth complexes. The fluorescence spectra and fluorescence lifetimes of the rare earth complexes show that the fluorescent intensity and lifetime of a series of europium complexes are longer than those of the series of terbium complexes as having the some ligands. There are better fluorescent intensity and lifetime of hetero-nuclear rare earth complexes than homo-nuclear rare earth complexes for europium complexes. The fluorescence emission intensity of Eu3+ is raised by inert fluorescent rare earth ions (Y3+, Gd3+ and La3+), but in Tb3+ hetero-nuclear rare earth complexes the intensity of Tb3+ ions are quenched by the inert fluorescent rare earth ions.
基金This work was financially supported by the Science Foundation of Hunan Province, China (No. 01C030)
文摘The fluorescence of terbium (Ⅲ) was enhanced by about three orders of magnitude in the presence of trimellitic acid (benzene-1, 2, 4-tricarboxylic acid (TLA)) in aqueous solution at pH 6. The fluorescence intensity could be greatly increased when the system of Tb^3+-TLA was treated with La^3+ (or Gd^3+) and TritonX- 100. The addition of La^3+ (or Gd^3+) enhanees the fluorescence of the system by about two orders of magnitude due to cofluorescenee, and the TritonX-100 micellar medium plays an important role for stabilization of the system. Both the intermolecular energy transfer mode and intramolecular energy transfer mode are responsible for the mechanism of fluorescence enhancement. In the optimum condi- tions, the fluorescence intensity is a linear function of Tb3~ concentration in the range of 7.8 × 10^-9-3.6 × 10^4 mol/L for the system Tb^3+-La^3+-TLA and 1.0 × 10^-8-4.7 × 10^-5 mol/L for the system Tb^3+-Gd^3+-TLA, and the limits of detection are 4.6 × 10^-10 mol/L and 6.0 × 10^-10 mol/L, respectively.
基金This work was supported by the Natural Science Foundation of Hebei Province (No. 203148 and No. 202140)
文摘A terbium benzoate complex with 1,10-phenanthroline [Tb(ba)3(phen)]2, where ba = benzoate and phen = 1,10-phenanthroline, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.7881(5), b = 11.9262(6), c = 12.4249(6) ?, a = 105.1260(10), β = 93.6010(10), ? = 113.3350(10)o, (C33H23N2O6Tb)2, Mr = 1404.90, V = 1391.87(12) ?3, Z = 1, Dc = 1.676 g/cm3, μ(MoKα) = 2.590 mm-1, F(000) = 696, the final R = 0.0277 and wR = 0.0670 for 6085 observed reflections with I > 2σ(I). The crystal consists of binuclear molecules of the title compound. Each Tb3+ ion is nine-coordinated to one 1,10-phenan- throline molecule, one bidentate carboxylate group and four bridging carboxylate groups. The carboxylate groups are bonded to the terbium ion in three modes: the chelating bidentate, bridging bidentate and bridging-chelating tridentates. Excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The results of thermal analysis indicate that the complex [Tb(ba)3phen]2 is very thermal stable.
基金The project is financially supported by the Natural Science Foundation of Hebei Province (No. 202140 and No. 203148)
文摘A terbium o-methylbenzoate complex with 1,10-phenanthroline, Tb(o-MBA)_3phen(where o-MBA = o-methylbenzoate and phen = 1,10-phenanthroline) was prepared from ethanol solutionand its crystal structure was determined by X-ray diffraction. The crystal of the complexTb(o-MBA)_3phen belongs to triclinic crystal system and P1 (#2) space group. The crystal data are asfollows: a = 1.4371(4) nm, b = 1.7387(2) nm, c = 1.3109(2) nm, α = 96.37(1)°, β = 107.21(2)°,γ= 82.78(2)°, Ⅴ= 3.094(1) nm^3, Z= 2, M_r = 1489.12, D_c= 1.598 g·cm^(-3), μ = 2.330 mm^(-1)and F(000) = 1488.00. The final R and R_w are 0.038 and 0.047 for 8668 [Ⅰ > 2σ(Ⅰ)] uniquereflections, respectively. In the complex each Tb^(3+) ion is eight-coordinated by one1,10-phenanthroline molecule, one bidentate carboxylate group and four bridging carboxylate groups.The carboxylate groups are bonded to the terbium ion in two modes: the chelating bidentate and thebridging bidentate. Excitation and luminescence data observed at room temperature show that thetitle complex emits strong green fluorescence under ultraviolet light. The results of thermalanalysis indicate that the complex Tb(o-MBA)_3phen is quite stable to heat.
文摘The binding of Tb 3+ to chicken apoovotransferrin was studied by monitoring the fluorescent intensity of Tb 3+ at 549 nm. The conditional equilibrium constants for the complexation of Tb 3+ by chicken apoovotransferrin in 0 1 mol/L hepes, at pH 7 4 and room temperature were measured. The successive macroscopic binding constants are lg K 1=9 08±0 12 and lg K 2=7 36±0 22. The molar fluorescence enhancement of Tb 3+ apoovotransferrin complex is (2 06±0 14)×10 4 mol -1 ·L. The fluorescence quenching experiment and the titration of N terminal monoferric ovotransferrin showed that Tb 3+ has a preference for being bound to the N terminal binding site of apoovotransferrin.
文摘The phenomenon of fluorescence enhancement for the system of terbium( Ⅲ ) with trimesic acid [ ben-zene-1, 3, 5-tricarboxylic acid (TMA)] in the presence of an excase of La ̄(3+) in gelatin aqusous solution wasstudied. The fluorescence intensity of Tb ̄Ⅲ -TMA system can be greatly increased by La ̄(3+) , which causedthe largest enhancement of the fluorescence intensity over two orders of magnitude. The intermolecular transfer of energy was responsible for the mechanism of the fluorascence enhancement. Gelatin plays animportant role for the stabilization of the system. The system, having the maximum excitation and emis-sion wavelengths at 260 nm and 549 nm, respectively, shows a constant fluorescence interisity over the pHrange 4~6. The fluorescence intensity is a linear function of Tb ̄(3+) concentration in the range of 8. 0 ×10  ̄(-9)~ 2. 6 × 10 ̄(-7) mol· L ̄(-1) and the limit of detection is 2.0 × 10 ̄(-9) mol·L ̄(-1) . The optimized procedurewas used for the determination of trace amount of terbium in rare earth oxides and international standardreference rocks with satisfactory results.
文摘Poly (N-vinylacetatnide) ( PNVA) was synthesized by free radical polymerization in ethanol solution, in which alpha, alpha'-azobisisobutyronitrile was used as an initiator. Tb(III)-PNVA polymer was prepared and characterized by ultraviolet-visual (UV), fourier transform infrared (FIF-IR), X-ray photoelectron spectroscopy (XPS) and fluorescence spectroscopy. The experimental results of UV, FT-IR and XPS show that the Tb (III)-PNVA electrovalent complex is formed by electrostatic interaction between terbium (III) cation and complexible atoms of acylamino group in the pendant chain of the polymer. The fluorescence spectrum of the complex exhibits intensive characteristic emission of terbium at 490, 545 and 584 run, which are assigned to D-5(4)->F-7(6), D-5(6)->F-5(6) and D-5(4)->F-7(3) transition, indicating that there exists an efficient intermolecular energy transfer from the polymer ligand to the central rare earth ion. The emission intensity of the complex is increased with the increasing concentration of Tb (III) ion until the weight ratio of Tb (III) on to PNVA is 1.5% (mass fraction), and decreased with the further increasing concentration of Tb (III) ion, which is a typical concentration quenching behavior.
基金Supported by the NSF of China(21361013,31460488)NSF of Fujian(2018J01447)+1 种基金Jiangxi Provincial Department of Education’s Item of Science and Technology(GJJ170637)the Open Foundation(20180008)of State Key Laboratory of Structural Chemistry
文摘A novel terbium-mercury complex [Tb(IA)3(H3 O)2]2 n(2 n HgCl4)(n Hg2 Cl5)·n H3 O· 3 n H2 O(1, HIA = isonicotinic acid) has been synthesized through hydrothermal reactions and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the C2/c space group of monoclinic system with a = 24.2347(5), b = 20.8342(6), c = 15.3206(3) ?, β = 128.257(2)°, V = 6074.3(2) ?3, C36H41Cl13Hg4N6O20Tb2, Mr = 2458.80, Z = 4, Dc = 2.689 g/cm3, μ(Mo Kα) = 13.014 mm–1 and F(000) = 4520. The crystal structure of 1 is characterized by a one-dimensional(1-D) chain-like structure. Solid-state UV/Vis diffuse reflectance spectrum reveals the existence of a wide optical band gap of 3.36 eV. Solid-state photoluminescence experiment uncovers that it shows reddish brown upconversion emission. The emission bands are originated from the characteristic emission of the 4 f electrons intrashell transition of the 5D4 → 7 FJ(J = 6, 5, 4) of the Tb3+ ions. Energy transfer mechanism is explained by the energy level diagram of the Tb3+ ion and the isonicotinic acid ligand. It shows a remarkable CIE chromaticity coordinates(0.4158, 0.4005).
文摘To understand the nature and behavior of rare earth metals in their liquid phases, accurate values of their physical properties are essential. However, to measure their physical properties, the samples should be maintained in liquid phases for prolonged time, and this raises a formidable challenge. This is mainly explained by their high melting temperatures (e.g., 1629 K for Tb), high vapor pressure, and the risk of melt contamination with a crucible or support. An electrostatic levitation furnace alleviated these difficulties and allowed the determination of density, surface tension, and viscosity of several metals above their melting temperature. Here, first, the levitation furnace facility and the noncontact diagnostic procedures were briefly discussed, followed by the explanation of their thermophysical property measurements over wide temperature ranges. The density was obtained using an ultraviolet-based imaging technique that allowed excellent illumination, even at elevated temperatures. Over the 1615 to 1880 K temperature span, the density measurements could be expressed as p(T) =7.84 × 10^3 -0.47 (T - Tm) (kg · m^-3) with Tm = 1629 K, yielding a volume expansion coefficient a(T) = 6.0 × 10^-5 (K^-1). In addition, the surface tension and the viscosity could be determined by inducing a drop oscillation to a molten sample. Using this technique, the surface tension data could be expressed as σ(T) = 8.93 × 10^2 - 0.10 (T - Tm)(mN· m^-1) and those for viscosity as η(T) =0.583 exp [4.1 × 10^4/(RT)] (MPa·s) over the 1690 to 1980 K temperature range
文摘Three new complexes TbL3dipy (H2O)2, TbL3phen (H2O) 2 and TbL2 (TPPO) 2NO3 were synthesized (L = phenylglyoxylate ion, dipy = 2, 2-dipyridine, phen = 1,10-phenanthmline, TPPO = Triphenyl phosphine oxide). Elemental analysis, conductivity, IR spectra, and ^1HNMR spectra studies were performed. IR spectra indicate that the carboxylate ion of phenylglyoxylate is coordinated to the Tb(Ⅲ) ion as an unidentate ligand. In ^1HNMR, the signals of different hydrogens in phenylglyoxylate ion shift upfield. The excitation and emission spectra of the three solid complexes were recorded at morn temperature, in which the optimum excitation wavelengths are, 361.0, 359.0 and 367.0 nm for these three complexes, respectively. Four emission bands due to the ^5D4-^7Fj(j = 6, 5, 4, 3) transitions were observed for TbL3dipy(H2O)2(489.0, 545.0, 584.0, 620.0 nm) and TbL3phen(H2O)2(490.0, 544.0, 583.0, 620.0 nm). Under the same conditions, only one emission band due to the ^5D4-^7F5 transition was observed for the complex TbL2(TPPO)2NO3. The emission intensity of TbL3dipy(H2O)2 is the strongest among the three complexes.
基金supported by Youth Fund of Nanyang Normal University(QN2017046)
文摘A dual functional coordination polymer, namely, {[Tb(mat)(1.5)H2O]·2.5H2O}n(1, H2mta = 2-methoxyterephthalic acid), was synthesized under solvothermal condition and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, X-ray powder diffraction analysis(PXRD), and thermogravimetric analysis(TGA). Complex 1 exhibits a 3D framework based on infinite rod-shaped secondary building units(SBUs). Furthermore, the solid-state luminescent property and magnetic properties of the complex were investigated at room temperature; the results show that the complex exhibits excellent luminescent properties in green luminescence and weak antiferromagentic behavior.
文摘Ethyl methacrylate (EMA) doped with luminescent ternary terbium complex (Tb(acac) 3·dam) with acetylacetone (Hacac) and diantipylmethane (dam) was incorporated into the microporous silica gel. With the polymerization of EMA, the hybrid material containing Tb(acac) 3·dam was obtained. The hybrid material exhibited good toughness and transparency and higher thermal stability than that of the pure complex and pure polymer matrix. In the range of doping concentration of Tb(acac) 3·dam (0.05%, 0.1%, 0.2%, 0.5%, 1.0%, 2.0% and 5.0%), emission intensity increases with the increasing of corresponding doping concentration and concentration quenching effect has not taken place.
基金supported by the Natural Science Foundation of Jiangxi Province (No. 0320026 and 0520036)the Natural Science Foundation of Jinggangshan University (No. JZ0815)
文摘A novel Tb(Ⅲ) coordination polymer [Tb(bpapO2)2(NO3)3]n [bpapO2 = N2,N6- bi(pyridin-2-yl)pyridine-2,6-diamine-N,N'-dioxide-dioxide] has been synthesized and it exhibits terbium’s characteristic fluorescent emission under UV radiation of 326 nm at room temperature. X-ray structural determination indicates that each terbium(Ⅲ) ion, centered in TbO8 core, connects to three adjacent coordinate centers via a bi-dentate ligand bpapO2, forming a one-dimensional coordination polymer. The compound crystallizes in the triclinic system, space group P1, with a = 11.2271(5), b = 11.7997(5), c = 14.8016(6) Ⅲ, α = 72.7060(10), β = 89.9630(10), γ = 66.7680(10)o, Z = 2, Dc = 1.822 g/cm3, V = 1705.14(13) Ⅲ3, F(000) = 932, the final R = 0.0340 and wR = 0.0669 for 4812 observed reflections with I 2σ(I).
基金SupportedbytheNationalScienceFoundationofChina (No .2 0 0 0 70 10 10 8)andWuhanMunicipalScience&TechnologyCommission (No .995 0 0 40 80 )
文摘This article describes a new method for the simultaneous determination of trace rare earth elements (REEs) and non rare earth elements (NREEs) in high purity terbium oxide by ICP-AES after HPLC separation using P507 resin. The chromatographic separation of the analytes from the matrix using dilute nitric acid as mobile phase was studied. The experimental results showed that a favorable separation of trace metals (Cu and Gd) from the matrix (Tb) can easily be achieved by elution with dilute nitric acid within 25 min. The proposed method was applied to the determination of trace metals (Ca, Cu, Mg, Mn, Ni, Si, La, Ce, Pr, Nd, Sm, Eu and Gd) in high purity terbium oxide. The detection limits (DLs) for the analytes ranged from 0.4-4.0 μg\5g -1, and the recoveries are from 78%-105%.
基金supported by the National Natural Science Foundation of China(No.21671114 and U1804131)Natural Science Foundation of Henan Province(No.182300410166,182102310909 and 182102310897)
文摘A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid(H4bptc) has been synthesized, {[Tb(Hbptc)(H2O)4]×H2O}n(1). Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. Title complex crystallizes in monoclinic, space group P21/n with a = 14.090(2), b = 8.0824(13), c = 15.5591(17) A, V = 1775.4(5) A3, Mr = 576.22, Dc = 2.156 g/cm3, μ(Mo Kα) = 4.059 mm-1, F(000) = 1128, Z = 4, the final R = 0.027 and w R = 0.0726 for 3296 observed reflections(I > 2σ(I)). Complex 1 exhibits a 2 D layer structure, and such layers are further united together into a three-dimensional supramolecular structure through π···π interaction and intricate hydrogen bonding. The fluorescence excitation and emission spectroscopy of 1 showed that H4 bptc is a kind of highly efficient sensitizer for terbium(Ⅲ) ion. The title complex also displays efficient ligand sensitized luminescence in the visible region with long lifetime of 2.02 ms in the solid state.
基金Supported by Henan Province Key Scientific Research Projects(122102210395)Pingdingshan Key Scientific Research Projects(No.2013066)
文摘A new coordination compound with formula [Tb(2-TC)3(DMF)]n (1, 2-TC = 2-thio- phenecarboxylic ligand and DMF = dimethylformamide) was synthesized by solvothermal method. The structure of compound 1 was determined by single-crystal X-ray diffraction analyses, and characterized by elemental analyses, IR and powder X-ray diffraction. Structure analysis reveals compound 1, exhibiting a one-dimensional chain structure, crystallizes in triclinic space group P21/c, with a = 9.2751(19), b = 16.490(3), c = 15.865(5) A, β = 118.98(2)°, V= 2122.7(9)A3, D,. = 1.916 g/cm3, Mr= 612.45 (C18H15NO7S3Tb), F(000) = 1196,μ(MoKa) = 3.67 mm-1, Z = 4, R = 0.0616 and wR = 0.0962 for 3865 observed reflections (I 〉 2o(I)), and R = 0.1092 for all data. Meanwhile, the photoluminescent properties of compound 1 were also investigated in the solid state at room temperature.
基金Project supported bythe Science Fund of Education Office in Jilin Province (200468)
文摘Tb(Ⅲ )-trimesic acid (TMA) luminescent complexes were synthesized in the polyvinylpyrrolidone (PVP) matrix. The elemental analysis, inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and fourier-transform infrared spectroscopy (FT-IR) indicated that its chemical constitution is PVP/Tb(MTA)· 4H2O. The XRD patterns showed that the complex is a new kind of crystal. The TEM image indicates that the complex is rod shaped. The rod diameter is about 200 nm, and the length ranges from hundred of nanometer to a few micrometers. In addition, the dispersity is better. TG-DTA curves indicate that the complex is thermally stable before 463℃. Photoluminescence analysis indicates that the complex emits Tb^3+ characteristic luminescence under ultraviolet excitation.
基金supported by the cooperative project of Hengyang Normal University with Hengyang Yile New Materials Co.,Ltd.(HXKJ201905)the Natural Science Foundation of Hunan Province(2019JJ60021,2019JJ50013)+1 种基金the Scientific Research Found of Hunan Provincial Education Department of China(17A049)the Industry and Research Key Project of Hengyang City(2018k KJ016,2017KJ155,2017KJ193)
文摘A new terbium(Ⅲ) complex Tb(C20H14O3N)3(C12H8N2)(H2O)·H2O has been synthesized with 2-diphenylanine carbonyl benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: triclinic, space group P1, a =11.6034(6), b = 16.2465(8), c = 16.4427(8) A, α = 73.168(5)°, β = 88.655(4)°, γ = 82.865(4)°, V = 2943.7(3)A^3, Dc = 1.494 g/cm^3, Z = 2, μ(MoK α) = 1.272 mm^-1, F(000) = 1348, the final R = 0.0535 and wR = 0.0809. The Tb(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry. The complex shows four fluorescence emission bands arising from the transitions of Tb^3+: 5D4 → 7F6(491 nm), 5D4 → 7F5(546 nm), 5D4 → 7F4(585 nm) and 5D4→7F3(621 nm). Also reported are the magnetic and thermal stability properties of the complex.