Binary and ternary terbium complexes were synthesized: Tb(N PA) 3·4H 2O and Tb(N PA) 3(phen·2H 2O (N HPA = N phenyl 2 aminobenzoic acid and phen = 1,10 phenanthroline). These complexes were introd...Binary and ternary terbium complexes were synthesized: Tb(N PA) 3·4H 2O and Tb(N PA) 3(phen·2H 2O (N HPA = N phenyl 2 aminobenzoic acid and phen = 1,10 phenanthroline). These complexes were introduced into inorganic polymeric porous silica matrix by the sol gel method. The luminescence behavior of the complexes in silica gels was compared with the corresponding solid state complexes by means of emission, excitation spectra and luminescence lifetimes. The result indicates that the terbium ions show fewer emission lines and lower emission intensities in the silica gel than those in pure terbium complexes. The lifetimes of terbium ions in silica gel doped with terbium complexes become longer than those of terbium complexes.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 Tb0.5 RE0.5(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
Abstract： Ten solid terbium complexes with 2-pyrazinecarboxylic acid （Hpyca） and butanedioic acid （BDAH） were synthesized via coprecipitation method and characterized by elemental, EDTA titration, inductively cou...Abstract： Ten solid terbium complexes with 2-pyrazinecarboxylic acid （Hpyca） and butanedioic acid （BDAH） were synthesized via coprecipitation method and characterized by elemental, EDTA titration, inductively coupled plasma （ICP）, thermogravim- etry-differential scanning calorimetry （TG-DSC） and infrared （IR） analyses. The results showed that the complexes had the composi- tions of Tb（pyca）（BDA）·2H2O, Tb0.5Y0.5（pyca）（BDA）·2H2O, Tb0.5La0.5（pyca）（BDA）·3H20, Tb0.5Gd0.5（pyca）（BDA）·2H2O, Tb0.7Y0.3（pyca）（BDA）·3HO, Tb0.7Lao.3（pyca）（BDA）-0.5H20, Tb0.TGd0.3（pyea）（BDA）＇H20, Tb0.6Y0.4（pyca）（BDA）·2.5H20, Tb0.6La0.4 （pyca）（BDA）·2.5H2O and Tbo.6Gd0.4（pyca）（BDA）·3H20. IR spectra indicated that the rare earth ions coordinated with the carboxylic oxygen atoms of Hpyca and BDAH. Luminescence spectra showed that the doped La3＋, y3＋ or Gd3＋ ions did not affect the lumines- cence emission peak positions, but remarkably increased the luminescent intensities of terbium complexes. Furthermore, the doped lanthanide complexes showed longer luminescence lifetimes and higher quantum yields than pure terbium complex. The enhanced luminescence efficiencies of Tb3＋ ions in the doped complexes might result from the antenna effect of the two carboxylate ligands as well as the decrease of the self-quench of the Tb3＋ ions induced by the doped lanthanide ions.展开更多
By modifying the salicylic-acid moiety with electron-withdrawing or –donating groups, three new terbium complexes（LⅠ·Tb, LⅡ·Tb, L·（Ⅲ）Tb） based on tripodal carboxylate ligands were synthesized. D...By modifying the salicylic-acid moiety with electron-withdrawing or –donating groups, three new terbium complexes（LⅠ·Tb, LⅡ·Tb, L·（Ⅲ）Tb） based on tripodal carboxylate ligands were synthesized. Due to different pull-push electronic effects of ligands, the fluorescence intensities of these terbium complexes significantly varied, that is： LⅡ·Tb 〉L（Ⅲ）·Tb〉 LⅠ·Tb. Meanwhile, the characteristic peaks at 492 nm（5D4→7F6） and 547 nm（5 D4→7F5） showed ＂Off–On–Off＂ fluorescence response to various p H conditions,which indicated that all of them can be used as the highly sensitive pH fluorescent probes. Notably, using LⅡ·Tb with the best fluorescence performance as a probe, some patients＇ urine samples can be easily monitored through the response triggered by pH value. Therefore, LⅡ·Tb has the potential to auxiliarily diagnose some diseases in clinical practice through p H detection of routine urine test.展开更多
Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were prepared. By replacing half of the europium or terbium ion with M （M = Zn^2＋, Cd^2＋, and Cr^3＋） using the dope...Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were prepared. By replacing half of the europium or terbium ion with M （M = Zn^2＋, Cd^2＋, and Cr^3＋） using the doped method, and then incorporating it with 18-crown-6 ether and terephthalic acid, six heteronuclear samples EuZnLL＇Cl3·3H2O（1）, EuCdLL2＇Cl3·5H2O（2）, EuCrLL＇Cl4· 4H2O（3）, TbZnLL＇Cl3·4H2O（4）, TbCdLL＇2Cl3·4H2O（5）, and TbCrLL＇2Cl4 ·4H2O（6） （L = terephthalic acid, L＇= 18-Crown-6 ether） were obtained. The elemental analysis, molar conductivities, rare earth complexometry, Fourier Transform Infrared Spectroscopy （FT-IR）, ultraviolet （UV）, TGA, fluorescence intensity, and fluorescence lifetime of the samples were measured. The results showed that there were good luminescence properties for heteronuclear complexes （1）, （2）, （4）, and （5）, which were even stronger than those of the homonuclear complexes Eu2LL＇2Cl4·4H2O and Tb2LL＇2Cl4 ·4H2O, but the luminescence properties of EuCrLL＇Cl4·4H2O, TbCrLL＇Cl4·4H2O were very weak. A possible luminescence mechanism was suggested by the organic-inorganic doped mechanism and the law of intramolecular energy transfer.展开更多
Silica gel luminophors containing 1, 10-phenanthroline-tris(M-Methylbenzoate) europium (or terbium) com- plexes were prepared bysol-gel method. The thermal decomposition, excitation and emissionspectra for the gel pho...Silica gel luminophors containing 1, 10-phenanthroline-tris(M-Methylbenzoate) europium (or terbium) com- plexes were prepared bysol-gel method. The thermal decomposition, excitation and emissionspectra for the gel phos- phors were measured and compared with thatof solid complex powders. The thermal stability of the complexes wasen- hanced in SiO_2 host matrix and the luminescence intensityremained unchanged.展开更多
The rare earth complexes Tb（o-BrBA）3,Tb（m-BrBA）3 and Tb（p-BrBA）3 were synthesized using o-,m-,p-bromo benzoic acids（2-bromo benzoic acid,3-bromo benzoic acid and 4-bromo benzoic acid） as ligand,respectively.Th...The rare earth complexes Tb（o-BrBA）3,Tb（m-BrBA）3 and Tb（p-BrBA）3 were synthesized using o-,m-,p-bromo benzoic acids（2-bromo benzoic acid,3-bromo benzoic acid and 4-bromo benzoic acid） as ligand,respectively.The UV spectra showed that the absorption ability of Tb（m-BrBA）3 was the strongest.However,the fluorescent intensity of Tb（o-BrBA）3 was the weakest.The effect of the molecular structure,the energy level of Tb3＋ and energy transfer efficiency from ligands to Tb3＋ were discussed to explain the experimental results.The results indicated that,due to the large atomic radius of bromine,the steric effect caused by the different substitution bromine on the benzene ring might strongly affect the bond length formed by the coordination atoms and Tb3＋.The longer the bond length was,the lower the efficiency of energy transfer was,and the weaker the fluorescent intensity was.展开更多
A reactive Tb（III） complex with 2-aminobenzoic acid（2-ABAH） and acrylonitrile（AN） as ligands was synthesized.The structure of the complex was characterized by elemental analysis and Fourier transform infrared sp...A reactive Tb（III） complex with 2-aminobenzoic acid（2-ABAH） and acrylonitrile（AN） as ligands was synthesized.The structure of the complex was characterized by elemental analysis and Fourier transform infrared spectrometry（FT-IR）.The results indicated that the ligands were coordinated with Tb（III） ion.Thermal gravity-derivative thermogravimetric（TG-DTG） analysis indicated that the complex kept stable up to 198 oC.Luminescence properties were investigated by UV-vis absorption spectra and fluorescence spectra.The results suggested that being excited at 361 nm,the complex exhibited characteristic emission of Tb（III） ion,revealing that the complex could be excited by 365 nm ultraviolet chip.The HOMO and LUMO,ΔE（HOMO-LUMO）,molecular frontier orbital,and the singlet state and triplet energy state levels of the ligands were calculated at the B3LYP/6-31＋G（d） level.The results indicated that intramolecular energy transfer mechanism followed Dexter exchange energy transfer theory.Both the calculation for excited state of ligand and energy transfer mechanism could provide the theoretical basis for the design of high luminescent materials of rare earth complexes with organic ligands.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
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
Rare earth complex TbY(m-MOBA)_6(phen)_2·2H_2O was synthesized, which was first used as an emitting material in electroluminescence. The properties of monolayer device with the rate of 1000 r·min^(-1) (70 nm...Rare earth complex TbY(m-MOBA)_6(phen)_2·2H_2O was synthesized, which was first used as an emitting material in electroluminescence. The properties of monolayer device with the rate of 1000 r·min^(-1) (70 nm) and the impure concentration of 1∶5 were the best. And the highest brightness of this device reached 21.8 cd·cm^(-2) at a fixed bias of 20 V. Bright green emission can be obtained from the optimized double-layer device, and the highest EL brightness of the device reached 289 cd·m^(-2) at the voltage of 21 V.展开更多
Three kinds of novel hydroxyapatite@terbium complex core-shell composites were synthesized with 2-chlorobenzoic acid,4-chlorobenzoic acid,and 2,4-dichlorobenzoic acid as the ligand,respectively.The XRD,UV/vis absorpti...Three kinds of novel hydroxyapatite@terbium complex core-shell composites were synthesized with 2-chlorobenzoic acid,4-chlorobenzoic acid,and 2,4-dichlorobenzoic acid as the ligand,respectively.The XRD,UV/vis absorption and FT-IR results show that terbium ions are coordinated with ligands and the corresponding complexes are successfully included into composites.SEM and EDS results reveal that Tb complexes are fully and homogenously coated on the surface of hydroxyapatite(HAP)microspheres consisting of a large number of nanosized crystals.The strongest luminescence properties are obtained when 2,4-dichlorobenzoic acid is used as ligand.The study on fluorescence lifetime of composites shows that the lifetime is inversely related to emission intensity.TGA-DSC results indicate that the core-shell composites have an excellent thermal stability.Therefore,the current core-shell structure provides a cost-effective route to manufacture of biocompatible and heatresistant highly luminescent materials.展开更多
The complex of [Tb（2-IBA）3（H2O）2]n （2-IBA=2-iodobenzoate） was prepared by solvent method from TbCl3-6H2O and 2-iodobenzoic acid. The crystal structure was determined with X-ray single-crystal diffraction. The X-...The complex of [Tb（2-IBA）3（H2O）2]n （2-IBA=2-iodobenzoate） was prepared by solvent method from TbCl3-6H2O and 2-iodobenzoic acid. The crystal structure was determined with X-ray single-crystal diffraction. The X-ray diffraction analysis indicated that the title complex crystallized in triclinic crystal system and Pi space group. The Tb^3＋ ion was coordinated by six oxygen atoms from five 2-IBA ligands and two oxygen atoms from two water molecules, giving a distorted square-antiprism polyhedral geometry. The carboxyl groups were bonded to the Tb^3＋ ions with bidentate-bridging and bidentate-chelating coordination modes. The adjacent Tb^3＋ ions were linked by two bidentate-bridging 2-IBA ligands, forming 1-D chain structure. The fluorescence spectrum of the complex showed four main peaks at 489, 543, 587, and 618 nm, corresponding to ^5D4→^7Fj（J=6-3） transition emissions of the Tb^3＋ ion, respectively.展开更多
The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 wi...The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a = 30.6840（1）, b = 10.9206（2）, c = 17.4967（3） A, β= 111.931（1）°, V = 5438.65（14） A^3, Z = 4, C46H52N6O25S2Tb2, Mr = 1470.90, Dc = 1.796 g/cm^3, p = 2.747 mm^-1, F（000） = 2928, the final R = 0.0654 and wR = 0.1322 for 3806 observed reflections with I 〉 2σ（I）. In the neutral [Tb（SIP）（H2O）5]2 motif, the Tb（III） ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H...N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.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 analysi...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） ?, V = 1775.4（5） ?3, 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 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: triclin...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） ?, α = 73.168（5）o, β = 88.655（4）o, γ = 82.865（4）o, V = 2943.7（3） ?3, Dc = 1.494 g/cm3, Z = 2, μ（MoK α） = 1.272 mm-1, F（000） = 1348, the final R = 0.0535 and w R = 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 Tb3+: 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
A complex of terbium(Ⅲ) with Schiff base salicylaldehyde-taurine and 1,10-phenanthroline was synthesized. The molecular formula was [Tb (sal-taurine) (1,10-phen) (NO_3)]·2H_2O (sal=salicylaldehyde, 1,10-phen=1,1...A complex of terbium(Ⅲ) with Schiff base salicylaldehyde-taurine and 1,10-phenanthroline was synthesized. The molecular formula was [Tb (sal-taurine) (1,10-phen) (NO_3)]·2H_2O (sal=salicylaldehyde, 1,10-phen=1,10-phenanthroline). The composition of the title complex was determined by elemental analysis and EDTA volumetic analysis. IR, Molar conductivity and X-ray powder diffraction were performed for its characterizations. The thermal decomposition kinetics of the complex were investigated under non-isothermal condition using the Achar differential method and the Coats-Redfern integral method. The kinetic equation for the second step corresponds to the mechanisms of the Zhuralev, Lesokin and Templman equation were obtained.展开更多
A new dinuclear Tb（Ⅲ） 4-cyanobenzoate complex [Tb2（4-cba）6（phen）2] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solut...A new dinuclear Tb（Ⅲ） 4-cyanobenzoate complex [Tb2（4-cba）6（phen）2] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C72H40N10O12Tb2, Mr=1554.98, triclinic Pi, a = 9.903（3）, b = 11.769（8）, c = 15.078（8）A, a = 111.42（12）, It = 96.37（19）, γ = 101-24（14）°, V= 1572（1）A3, Z= 1, Dc = 1.642 g/cm^3, F（000） = 768 μ = 2.305 mm^-1, the final R = 0.0205 and wR = 0.0543 for 5479 reflections with I 〉 2σ（I）. Structural analysis shows that 1 displays an isolated dinuclear structure. Two eight-coordinated Tb（Ⅲ） ions are bridged by four 4-cba ligands in the syn-syn bidentate coordination mode, and two other 4-cba ligands chelate these two Tb（Ⅲ） ions. The title complex molecules are connected through π-π stacking interactions to generate a one-dimensional supramolecular chain, The characteristic infrared spectra, luminescent properties and thermogravimetric analyses have also been discussed.展开更多
A new rare earth complex Tb(p-MBA)_3phen was synthesized, which is first used as an emitting material in organic electroluminescence. By doping it into the conjugated polymer PVK, single-layer and double-layer devices...A new rare earth complex Tb(p-MBA)_3phen was synthesized, which is first used as an emitting material in organic electroluminescence. By doping it into the conjugated polymer PVK, single-layer and double-layer devices were fabricated with structures: device 1: ITO/PVK∶Tb(p-MBA)_3phen/Al; device 2∶ ITO/PVK: Tb(p-MBA)_3phen/AlQ/LiF/Al. The characteristics of these devices have been investigated. The emission of PVK is completely restrained, and only the pure green emission from Tb^(3+) can be observed in electroluminescence. The optimized device 2 has better monochromatic characteristics with the maximal brightness of 152 cd·m^(-2) at the voltage of 20 V.展开更多
Rare earth complex with a structure of [Tb(m-MBA)_3phen]_2·2H_2O was synthesized,which was used as light-emitting material in electroluminescence. The terbium complex was dispersed in poly (N-vinylcarbazole) (PVK...Rare earth complex with a structure of [Tb(m-MBA)_3phen]_2·2H_2O was synthesized,which was used as light-emitting material in electroluminescence. The terbium complex was dispersed in poly (N-vinylcarbazole) (PVK) as an emitting layer which is made by spin coating. Two kinds of devices were fabricated with structures: as following device Ⅰ: glass/ITO/PVK: terbium complex/PBD/LiF/Al, and device Ⅱ: glass/ITO/PVK: terbium complex/AlQ/LiF/Al. The photoluminescent (PL) and electroluminescent (EL) behaviors of the devices were investigated. Bright green emission can be obtained from optimized device Ⅱ,and the highest EL brightness of it reaches 140 cd·m (-2) at the voltage of 20 V.展开更多
文摘Binary and ternary terbium complexes were synthesized: Tb(N PA) 3·4H 2O and Tb(N PA) 3(phen·2H 2O (N HPA = N phenyl 2 aminobenzoic acid and phen = 1,10 phenanthroline). These complexes were introduced into inorganic polymeric porous silica matrix by the sol gel method. The luminescence behavior of the complexes in silica gels was compared with the corresponding solid state complexes by means of emission, excitation spectra and luminescence lifetimes. The result indicates that the terbium ions show fewer emission lines and lower emission intensities in the silica gel than those in pure terbium complexes. The lifetimes of terbium ions in silica gel doped with terbium complexes become longer than those of terbium complexes.
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 Tb0.5 RE0.5(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Project supported by National Natural Science Foundation of China(21161013)Natural Science Foundation of Inner Mongolia(2011MS0202)+1 种基金the Opening Foundation for Significant Fundamental Research of Inner Mongolia(2010KF03)financial supported and from the Inner Mongolia University"211project"innovative training project
文摘Abstract： Ten solid terbium complexes with 2-pyrazinecarboxylic acid （Hpyca） and butanedioic acid （BDAH） were synthesized via coprecipitation method and characterized by elemental, EDTA titration, inductively coupled plasma （ICP）, thermogravim- etry-differential scanning calorimetry （TG-DSC） and infrared （IR） analyses. The results showed that the complexes had the composi- tions of Tb（pyca）（BDA）·2H2O, Tb0.5Y0.5（pyca）（BDA）·2H2O, Tb0.5La0.5（pyca）（BDA）·3H20, Tb0.5Gd0.5（pyca）（BDA）·2H2O, Tb0.7Y0.3（pyca）（BDA）·3HO, Tb0.7Lao.3（pyca）（BDA）-0.5H20, Tb0.TGd0.3（pyea）（BDA）＇H20, Tb0.6Y0.4（pyca）（BDA）·2.5H20, Tb0.6La0.4 （pyca）（BDA）·2.5H2O and Tbo.6Gd0.4（pyca）（BDA）·3H20. IR spectra indicated that the rare earth ions coordinated with the carboxylic oxygen atoms of Hpyca and BDAH. Luminescence spectra showed that the doped La3＋, y3＋ or Gd3＋ ions did not affect the lumines- cence emission peak positions, but remarkably increased the luminescent intensities of terbium complexes. Furthermore, the doped lanthanide complexes showed longer luminescence lifetimes and higher quantum yields than pure terbium complex. The enhanced luminescence efficiencies of Tb3＋ ions in the doped complexes might result from the antenna effect of the two carboxylate ligands as well as the decrease of the self-quench of the Tb3＋ ions induced by the doped lanthanide ions.
基金supported by the National Natural Science Foundation of China (Nos. 21572091 and 21472075)the Fundamental Research Funds for the Central Universities (No. lzujbky-2016-51) by Ministry of Education of China
文摘By modifying the salicylic-acid moiety with electron-withdrawing or –donating groups, three new terbium complexes（LⅠ·Tb, LⅡ·Tb, L·（Ⅲ）Tb） based on tripodal carboxylate ligands were synthesized. Due to different pull-push electronic effects of ligands, the fluorescence intensities of these terbium complexes significantly varied, that is： LⅡ·Tb 〉L（Ⅲ）·Tb〉 LⅠ·Tb. Meanwhile, the characteristic peaks at 492 nm（5D4→7F6） and 547 nm（5 D4→7F5） showed ＂Off–On–Off＂ fluorescence response to various p H conditions,which indicated that all of them can be used as the highly sensitive pH fluorescent probes. Notably, using LⅡ·Tb with the best fluorescence performance as a probe, some patients＇ urine samples can be easily monitored through the response triggered by pH value. Therefore, LⅡ·Tb has the potential to auxiliarily diagnose some diseases in clinical practice through p H detection of routine urine test.
基金Project supported by the National Natural Science Foundation of China (20461002) Chun Hui Plan Foundation of MOE(Z2004-2-15029)
文摘Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were prepared. By replacing half of the europium or terbium ion with M （M = Zn^2＋, Cd^2＋, and Cr^3＋） using the doped method, and then incorporating it with 18-crown-6 ether and terephthalic acid, six heteronuclear samples EuZnLL＇Cl3·3H2O（1）, EuCdLL2＇Cl3·5H2O（2）, EuCrLL＇Cl4· 4H2O（3）, TbZnLL＇Cl3·4H2O（4）, TbCdLL＇2Cl3·4H2O（5）, and TbCrLL＇2Cl4 ·4H2O（6） （L = terephthalic acid, L＇= 18-Crown-6 ether） were obtained. The elemental analysis, molar conductivities, rare earth complexometry, Fourier Transform Infrared Spectroscopy （FT-IR）, ultraviolet （UV）, TGA, fluorescence intensity, and fluorescence lifetime of the samples were measured. The results showed that there were good luminescence properties for heteronuclear complexes （1）, （2）, （4）, and （5）, which were even stronger than those of the homonuclear complexes Eu2LL＇2Cl4·4H2O and Tb2LL＇2Cl4 ·4H2O, but the luminescence properties of EuCrLL＇Cl4·4H2O, TbCrLL＇Cl4·4H2O were very weak. A possible luminescence mechanism was suggested by the organic-inorganic doped mechanism and the law of intramolecular energy transfer.
基金This project is financially supported by Natural Science Foundation of Hebei Province, China (No. 299193)
文摘Silica gel luminophors containing 1, 10-phenanthroline-tris(M-Methylbenzoate) europium (or terbium) com- plexes were prepared bysol-gel method. The thermal decomposition, excitation and emissionspectra for the gel phos- phors were measured and compared with thatof solid complex powders. The thermal stability of the complexes wasen- hanced in SiO_2 host matrix and the luminescence intensityremained unchanged.
基金Project supported by the National Natural Science Foundation of China (50973003)Anhui Science and Technology Program (090518026)+1 种基金Natural Science Foundation of Fuyang Normal College (2011CXY04,2009FSKJ04,2011HJJC02ZD,2011HJJC01ZD,2011HJJC05YB,2011HJJC04YB,2011HJJC03YB,2010FSKJ01ZD)Open fund of State Key Laboratory of Rare Earth Materials Chemistry and Applications (RE201101)
文摘The rare earth complexes Tb（o-BrBA）3,Tb（m-BrBA）3 and Tb（p-BrBA）3 were synthesized using o-,m-,p-bromo benzoic acids（2-bromo benzoic acid,3-bromo benzoic acid and 4-bromo benzoic acid） as ligand,respectively.The UV spectra showed that the absorption ability of Tb（m-BrBA）3 was the strongest.However,the fluorescent intensity of Tb（o-BrBA）3 was the weakest.The effect of the molecular structure,the energy level of Tb3＋ and energy transfer efficiency from ligands to Tb3＋ were discussed to explain the experimental results.The results indicated that,due to the large atomic radius of bromine,the steric effect caused by the different substitution bromine on the benzene ring might strongly affect the bond length formed by the coordination atoms and Tb3＋.The longer the bond length was,the lower the efficiency of energy transfer was,and the weaker the fluorescent intensity was.
基金Project supported by the Program for Changjiang Scholar and Innovative Research Team in University (IRT0972)the International Cooperation Program of Shanxi Province (2009081046)the Postgraduate Innovation Program of Shanxi Province (20103023)
文摘A reactive Tb（III） complex with 2-aminobenzoic acid（2-ABAH） and acrylonitrile（AN） as ligands was synthesized.The structure of the complex was characterized by elemental analysis and Fourier transform infrared spectrometry（FT-IR）.The results indicated that the ligands were coordinated with Tb（III） ion.Thermal gravity-derivative thermogravimetric（TG-DTG） analysis indicated that the complex kept stable up to 198 oC.Luminescence properties were investigated by UV-vis absorption spectra and fluorescence spectra.The results suggested that being excited at 361 nm,the complex exhibited characteristic emission of Tb（III） ion,revealing that the complex could be excited by 365 nm ultraviolet chip.The HOMO and LUMO,ΔE（HOMO-LUMO）,molecular frontier orbital,and the singlet state and triplet energy state levels of the ligands were calculated at the B3LYP/6-31＋G（d） level.The results indicated that intramolecular energy transfer mechanism followed Dexter exchange energy transfer theory.Both the calculation for excited state of ligand and energy transfer mechanism could provide the theoretical basis for the design of high luminescent materials of rare earth complexes with organic ligands.
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.
文摘Rare earth complex TbY(m-MOBA)_6(phen)_2·2H_2O was synthesized, which was first used as an emitting material in electroluminescence. The properties of monolayer device with the rate of 1000 r·min^(-1) (70 nm) and the impure concentration of 1∶5 were the best. And the highest brightness of this device reached 21.8 cd·cm^(-2) at a fixed bias of 20 V. Bright green emission can be obtained from the optimized double-layer device, and the highest EL brightness of the device reached 289 cd·m^(-2) at the voltage of 21 V.
基金Project supported by the Major Project of Natural Science Research in Universities of Anhui Province(KJ2018ZD037,KJ2016A550)Horizontal Cooperation Project of Fuyang Municipal Government and Fuyang Normal University(XDHX201717,XDHX2016011,XDHX2016004)。
文摘Three kinds of novel hydroxyapatite@terbium complex core-shell composites were synthesized with 2-chlorobenzoic acid,4-chlorobenzoic acid,and 2,4-dichlorobenzoic acid as the ligand,respectively.The XRD,UV/vis absorption and FT-IR results show that terbium ions are coordinated with ligands and the corresponding complexes are successfully included into composites.SEM and EDS results reveal that Tb complexes are fully and homogenously coated on the surface of hydroxyapatite(HAP)microspheres consisting of a large number of nanosized crystals.The strongest luminescence properties are obtained when 2,4-dichlorobenzoic acid is used as ligand.The study on fluorescence lifetime of composites shows that the lifetime is inversely related to emission intensity.TGA-DSC results indicate that the core-shell composites have an excellent thermal stability.Therefore,the current core-shell structure provides a cost-effective route to manufacture of biocompatible and heatresistant highly luminescent materials.
基金supported by the Natural Science Foundation of Beijing (2073022)
文摘The complex of [Tb（2-IBA）3（H2O）2]n （2-IBA=2-iodobenzoate） was prepared by solvent method from TbCl3-6H2O and 2-iodobenzoic acid. The crystal structure was determined with X-ray single-crystal diffraction. The X-ray diffraction analysis indicated that the title complex crystallized in triclinic crystal system and Pi space group. The Tb^3＋ ion was coordinated by six oxygen atoms from five 2-IBA ligands and two oxygen atoms from two water molecules, giving a distorted square-antiprism polyhedral geometry. The carboxyl groups were bonded to the Tb^3＋ ions with bidentate-bridging and bidentate-chelating coordination modes. The adjacent Tb^3＋ ions were linked by two bidentate-bridging 2-IBA ligands, forming 1-D chain structure. The fluorescence spectrum of the complex showed four main peaks at 489, 543, 587, and 618 nm, corresponding to ^5D4→^7Fj（J=6-3） transition emissions of the Tb^3＋ ion, respectively.
基金the Education Department of Jiangxi Province (No. 2007-125)the Initial Fund for Doctors from Jiangxi Normal University
文摘The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a = 30.6840（1）, b = 10.9206（2）, c = 17.4967（3） A, β= 111.931（1）°, V = 5438.65（14） A^3, Z = 4, C46H52N6O25S2Tb2, Mr = 1470.90, Dc = 1.796 g/cm^3, p = 2.747 mm^-1, F（000） = 2928, the final R = 0.0654 and wR = 0.1322 for 3806 observed reflections with I 〉 2σ（I）. In the neutral [Tb（SIP）（H2O）5]2 motif, the Tb（III） ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H...N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.
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） ?, V = 1775.4（5） ?3, 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 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） ?, α = 73.168（5）o, β = 88.655（4）o, γ = 82.865（4）o, V = 2943.7（3） ?3, Dc = 1.494 g/cm3, Z = 2, μ（MoK α） = 1.272 mm-1, F（000） = 1348, the final R = 0.0535 and w R = 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 Tb3+: 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.
文摘A complex of terbium(Ⅲ) with Schiff base salicylaldehyde-taurine and 1,10-phenanthroline was synthesized. The molecular formula was [Tb (sal-taurine) (1,10-phen) (NO_3)]·2H_2O (sal=salicylaldehyde, 1,10-phen=1,10-phenanthroline). The composition of the title complex was determined by elemental analysis and EDTA volumetic analysis. IR, Molar conductivity and X-ray powder diffraction were performed for its characterizations. The thermal decomposition kinetics of the complex were investigated under non-isothermal condition using the Achar differential method and the Coats-Redfern integral method. The kinetic equation for the second step corresponds to the mechanisms of the Zhuralev, Lesokin and Templman equation were obtained.
基金the National Natural Science Foundation of China (20671091) Natural Science of Fujian Province (A0420002 and 2005I017)
文摘A new dinuclear Tb（Ⅲ） 4-cyanobenzoate complex [Tb2（4-cba）6（phen）2] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C72H40N10O12Tb2, Mr=1554.98, triclinic Pi, a = 9.903（3）, b = 11.769（8）, c = 15.078（8）A, a = 111.42（12）, It = 96.37（19）, γ = 101-24（14）°, V= 1572（1）A3, Z= 1, Dc = 1.642 g/cm^3, F（000） = 768 μ = 2.305 mm^-1, the final R = 0.0205 and wR = 0.0543 for 5479 reflections with I 〉 2σ（I）. Structural analysis shows that 1 displays an isolated dinuclear structure. Two eight-coordinated Tb（Ⅲ） ions are bridged by four 4-cba ligands in the syn-syn bidentate coordination mode, and two other 4-cba ligands chelate these two Tb（Ⅲ） ions. The title complex molecules are connected through π-π stacking interactions to generate a one-dimensional supramolecular chain, The characteristic infrared spectra, luminescent properties and thermogravimetric analyses have also been discussed.
文摘A new rare earth complex Tb(p-MBA)_3phen was synthesized, which is first used as an emitting material in organic electroluminescence. By doping it into the conjugated polymer PVK, single-layer and double-layer devices were fabricated with structures: device 1: ITO/PVK∶Tb(p-MBA)_3phen/Al; device 2∶ ITO/PVK: Tb(p-MBA)_3phen/AlQ/LiF/Al. The characteristics of these devices have been investigated. The emission of PVK is completely restrained, and only the pure green emission from Tb^(3+) can be observed in electroluminescence. The optimized device 2 has better monochromatic characteristics with the maximal brightness of 152 cd·m^(-2) at the voltage of 20 V.
文摘Rare earth complex with a structure of [Tb(m-MBA)_3phen]_2·2H_2O was synthesized,which was used as light-emitting material in electroluminescence. The terbium complex was dispersed in poly (N-vinylcarbazole) (PVK) as an emitting layer which is made by spin coating. Two kinds of devices were fabricated with structures: as following device Ⅰ: glass/ITO/PVK: terbium complex/PBD/LiF/Al, and device Ⅱ: glass/ITO/PVK: terbium complex/AlQ/LiF/Al. The photoluminescent (PL) and electroluminescent (EL) behaviors of the devices were investigated. Bright green emission can be obtained from optimized device Ⅱ,and the highest EL brightness of it reaches 140 cd·m (-2) at the voltage of 20 V.
