The binary europium complex EuL3 （L=4-tert-butylbenzoate） and ternary europium complexes EuL3TTAo.I （TTA=2- thenoyltrifluoroacetone）, EuL3DBMo.5 （DBM=dibenzoylmethane） and EuL3pheno.5 （phen=l, 10-phenanthroline...The binary europium complex EuL3 （L=4-tert-butylbenzoate） and ternary europium complexes EuL3TTAo.I （TTA=2- thenoyltrifluoroacetone）, EuL3DBMo.5 （DBM=dibenzoylmethane） and EuL3pheno.5 （phen=l, 10-phenanthroline） were synthesized. The poly（methyl methacrylate） （PMMA） or copolymer of methyl methacrylate （MMA） with acrylic acid （AA） composites doped with europium complexes were prepared by radical in-situ polymerization. The influences of the europium complexes, ligands, N,N-dimethylformamide （DMF） and monomers on the luminescence properties of the doped polymers were investigated. The results showed that the fluorescence excitation bands of binary and ternary complexes were in accordance with their ultraviolet absorption bands. All the complexes and the doped polymer composites exhibited the ligand-sensitized red characteristic emission of Eu3＋ ion. The fluorescence intensity of the polymer composites increased in the sequence of EuL3/PMMA〈EuL3pheno.5/PMMA〈EuL3DBMo.5/ PMMA〈EuL3TTAo.I/PMMA. It indicated that the introduction of a small amount of I^-diketone ligand affected the optimum excita- tion wavelength and the fluorescence intensity of polymer composites. Furthermore, DMF remarkably increased the luminescence intensity and transparence of the doped polymer composites. However, introduction of acrylic acid comonomer decreased the lumi- nescence intensity of the polymer composites.展开更多
A new complex of {[Eu2(2-BrBA)6(2,2’-bpy)2]2·CH3CH2OH·H2O} (2-BrBA=2-bromobenzoate; 2,2’-bpy=2,2’-bipyridine) was prepared by solvent method and characterized with X-ray single-crystal diffraction, IR spe...A new complex of {[Eu2(2-BrBA)6(2,2’-bpy)2]2·CH3CH2OH·H2O} (2-BrBA=2-bromobenzoate; 2,2’-bpy=2,2’-bipyridine) was prepared by solvent method and characterized with X-ray single-crystal diffraction, IR spectroscopy, UV spectroscopy, and fluorescence spectroscopy. The complex crystallized in triclinic crystal system, Pī space group, with a=1.17196(4) nm, b=2.36142(9) nm, c=2.59151(9) nm, α=113.266(2)°, β=101.100(2)°, and γ=94.400(2)°. Two independent dinuclear molecules were contained in the asymmetric unit. The two molecules were similar to each other. Each Eu(Ⅲ) ion was nine-coordinated with seven oxygen atoms from five 2-BrBA ligands and two nitrogen atoms from 2,2’-bpy molecule. The carboxylate groups acted as bidentate-chelating, bidentate-bridging and chelating-bridging coordination modes. The complex adopted a distorted monocapped square-antiprism coordination geometry. Five peaks at 579, 591, 613, 652, and 697 nm appeared in the fluorescence spectrum, corresponding to 5D0→7F0, 5D0→7F1, 5D0→7F2, 5D0→7F3, and 5D0→7F4 transition emissions of the Eu(Ⅲ) ion, respectively.展开更多
Dipyrido [3, 2-a:2,3-c] phenazine moiety has been introduced as neutral ligand in europium complex. Therefore, a new europium complex with saturated emission, strong fluorescent intensity and good solubility was desi...Dipyrido [3, 2-a:2,3-c] phenazine moiety has been introduced as neutral ligand in europium complex. Therefore, a new europium complex with saturated emission, strong fluorescent intensity and good solubility was designed and synthesized for the first time. Its photoluminescence and UV properties were examined. The experimental results showed that this new Eu-complex could be used as red electroluminescent materials.展开更多
A new europium（Ⅲ） complex, tris（dibertzoylmethanate）{ 1-[9-hexyl-9-carbazole]-2-（2-pyridyl）-bertzimidazole}europium（Ⅲ） [Eu（DBM）a（CPyBM）] was synthesized and used as an electron-acceptor and electron-tran...A new europium（Ⅲ） complex, tris（dibertzoylmethanate）{ 1-[9-hexyl-9-carbazole]-2-（2-pyridyl）-bertzimidazole}europium（Ⅲ） [Eu（DBM）a（CPyBM）] was synthesized and used as an electron-acceptor and electron-transport layer in organic photovoltaic （PV） device. Power conversion efficiency achieved from the device was 1.04% under illumination with 365 nm UV light at 1.6 mW/cm^2. Compared with the previous reported devices based on Eu（Ⅲ） complexes, the PV performances were improved. The working mechanism of the organic PV device was discussed.展开更多
The complex [Eu（3-IBA）3·2,2＇-bipy]2 was synthesized from 3-iodobenzoic acid （3-HIBA）, 2,2＇-bipyridine （2,2‘-bipy） and EuCl3·6H2O by hydrothermal synthesis, and its crystal structure was determined b...The complex [Eu（3-IBA）3·2,2＇-bipy]2 was synthesized from 3-iodobenzoic acid （3-HIBA）, 2,2＇-bipyridine （2,2‘-bipy） and EuCl3·6H2O by hydrothermal synthesis, and its crystal structure was determined by X-ray single-crystal diffraction. It is of triclinic, space group Pi, with a = 10.958（2）, b = 12.311（3）, c = 12.556（3） A, α = 81.549（3）, β = 82.404（4）, γ = 78.348（3）°, Mr = 1049.15, V= 1631.7（6） A3, Z = 1, Dc = 2.135 g/cm^3, F（000） = 980, 2（MoKa） = 0.71073 A,μ（MoKa） = 4.804 mm^-1, the final R = 0.0329 and wR = 0.0723 for 4640 observed reflections with I 〉 2σ（I）. The Eu（Ⅲ） ion is eight-coordinated and two Eu（Ⅲ） ions are held together by four 3-iodobenzoate groups in the bidentate bridging mode. The complex was characterized by DTA-TG, IR, UV and fluorescence spectra.展开更多
A novel dendritic europium complex containing grafted carbazole units as functional peripheries was synthesized and characterized. The Foerster energy transfer from the peripheries of carbazole units to β-diketonate ...A novel dendritic europium complex containing grafted carbazole units as functional peripheries was synthesized and characterized. The Foerster energy transfer from the peripheries of carbazole units to β-diketonate as well as from the hgands to the central Eu（Ⅲ） ions in the complex was demonstrated. Under the excitation of carbazole units and β-diketonate, characteristic red emission peaks at 612 nm with four shoulders due to the Eu（Ⅲ） ion transition of 5^D0→7^FJ （J=0-4） were observed for the complex.展开更多
A new europium complex Eu(tta)_(3)Li(la)based on 1,10-phenanthroline derivative(Li=(2-(3,5-dimethoxyphenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline),tta=2-thenoyItrifluoroacetone)was designed and synthesized.Its struct...A new europium complex Eu(tta)_(3)Li(la)based on 1,10-phenanthroline derivative(Li=(2-(3,5-dimethoxyphenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline),tta=2-thenoyItrifluoroacetone)was designed and synthesized.Its structure was characterized by^(1)H and^(13)C NMR,elemental analysis,UV-vis,fluorescence spectra and single crystal X-ray diffraction.The crystal of the complex la belongs to monoclinic system with the space group P2_(1/n).The europium complex la in the solid and in the solution displays the typical emission of Eu(III)ion centered at 612 nm as a result of the electric dipole transition(^(5)D_(0)-►^(7)F_(2)).It exhibits high quantum yield(20.42%),long lifetime(0.29 ms)and good CIE color coordinate(0.67,0.33)in solid.In addition,the complex shows high sensitivity and selectivity towards Al^(3+)and Zn^(2+)in methanol solution which can be attributed to the Al^(3+)/Zn^(2+)cation instead of Eu^(3+)in the complex la.The LODs for Al^(3+)and Zn^(2+)were calculated to be 5.880×10^(-7)and 7.678×10^(-8)mol/L,respectively.Besides,the additions of Al^(3+)and Zn^(2+)express remarkable color changes from red to bright blue and ivory that can be clearly observed by the naked eye respectively.展开更多
A novel organic ligand, 6 (ortho methyl anilino carbonyl) 2 pyridine carboxylic acid (H o MAP), and the corresponding europium complex, tris(6 (ortho methyl anilino carbonyl) 2 pyridine carboxylato) europium...A novel organic ligand, 6 (ortho methyl anilino carbonyl) 2 pyridine carboxylic acid (H o MAP), and the corresponding europium complex, tris(6 (ortho methyl anilino carbonyl) 2 pyridine carboxylato) europium (Eu o MAP) were designed and synthesized. The results show that solid Eu o MAP is a conjugated complex, emitting strong red fluorescence dominantly due to a ligand sensitizd luminescence mechanism. The lifetimes of 5D 0 of Eu 3+ in the complex were examined using time-resolved spectroscopic analysis, and the lifetime values were (1.50±0.01) ms for solid Eu(o MAP) 3 and (1.10±0.01) ms for 1.0×10 -5 mol·L -1 Eu(o MAP) 3 ethanol solution, respectively. Thermogravimetric analysis shows that the europium complex has good thermal stability.展开更多
A new chain europium complex [Eu(2,3-DFBA)3·(H2O)2]n(2,3-DFBA=2,3-difluorobenzoate) was synthesized by solvent method.X-ray single-crystal diffraction analysis revealed that Eu3+ ions were linked through 2,3-DFBA...A new chain europium complex [Eu(2,3-DFBA)3·(H2O)2]n(2,3-DFBA=2,3-difluorobenzoate) was synthesized by solvent method.X-ray single-crystal diffraction analysis revealed that Eu3+ ions were linked through 2,3-DFBA groups via alternate bidentate-bridging and tridentate chelating-bridging coordination modes to form a one-dimensional(1-D) polymeric chain.Each Eu3+ ion is eight-coordinated by six O atoms of five 2,3-DFBA ligands and two water molecules.The abundant hydrogen bonds between chains resulted in a two...展开更多
A new complex Eu2（PA）6（phen）2 was prepared with hydrothermal reaction using EuCl3.6H2O, phenylmalonic acid （H2phma）, and 1, 10-phenanthroline （phen）, where PA was the decarboxylated product of HEphma, phenylac...A new complex Eu2（PA）6（phen）2 was prepared with hydrothermal reaction using EuCl3.6H2O, phenylmalonic acid （H2phma）, and 1, 10-phenanthroline （phen）, where PA was the decarboxylated product of HEphma, phenylacetate. The crystal structure of the title complex was determined with the X-ray diffraction. The title complex was a binuclear molecule with an inversion center. Each Eu^3＋ ion was nine-coordinated with two nitrogen atoms from one phen molecule and seven oxygen atoms from five PA ligands. The carboxylic groups were bonded to the Eu^3＋ ion in three modes, the chelating bidentate, the bridging bidentate, and the bridging-chelating tridentate. The complex emits intense red fluorescence under ultraviolet light. The luminescence peaks correspond to the characteristic emission 5D0→7FJ （J=0-4） transitions of the Eu^3＋ ion.展开更多
A series of euroPium(Ⅱ)eomPlexes with earboxylie aeids andl,10-Phenantl飞ro-line:Eu(L):·pllen·jHoO,wl:ereL-formate,3-hydroxy-4-metlloxybenzoate,4一metl、oxybenzoate,4一ehloroPhenoxyaeetate,and diPI、enylaee...A series of euroPium(Ⅱ)eomPlexes with earboxylie aeids andl,10-Phenantl飞ro-line:Eu(L):·pllen·jHoO,wl:ereL-formate,3-hydroxy-4-metlloxybenzoate,4一metl、oxybenzoate,4一ehloroPhenoxyaeetate,and diPI、enylaeetate,were synthesizedand el、araeterized by elemental analysis,UV sPeetrum,IR speetrum and melting point.IR da亡a eonfirmed tllat euroPium 15 eoordinated wirh 0 donor atoms in earboxy!ie aeidand N donor atoms inl,10一phenanthroline.A strong ligand一loealized absorption at270 nm!ed to a series of meta!一eentered emission bands between 580 and 710 nm as-signedto ~5D_0-7F_(0.1.2.3.)展开更多
Tris (thenoyltrifluoroacetonato) mono(9-octadecylamino-4,5-diazafluorene) europium (III) was synthesized. Stable floating monolayer on pure water subphase (18 degrees C, pH 5.6) was obtained with a collapse pressure o...Tris (thenoyltrifluoroacetonato) mono(9-octadecylamino-4,5-diazafluorene) europium (III) was synthesized. Stable floating monolayer on pure water subphase (18 degrees C, pH 5.6) was obtained with a collapse pressure of 40 mN/m and a zero-pressure area of 0.495 nm(2) molecule(-1). The monolayers can be transferred onto hydrophilically treated substrates of quartz, calcium fluoride at a surface pressure of 25 mN/m with a transfer ratio of ca. unity. The films were characterized by UV, IR and fluorescent spectroscopy.展开更多
Using 2＇-Hydroxyacetophenone and as the raw material, 1-（ 2-Hydroxyphenyl ）-3-Phenyl-1, 3- Propanedione （HPPPD） was synthesized by esterification reaction and Fries rearrangement reaction. And the complexes of HP...Using 2＇-Hydroxyacetophenone and as the raw material, 1-（ 2-Hydroxyphenyl ）-3-Phenyl-1, 3- Propanedione （HPPPD） was synthesized by esterification reaction and Fries rearrangement reaction. And the complexes of HPPPD with europium were also synthesized. The compounds were characterized by IR, thermo-gravimetric analysis and ^1H-NMR. The effects of phenolic hydroxyl on the luminescence properties of complexes were studied. The results show that the complexes emit strong red fluorescence and the fluorescence intensity of the ternary complex is better than that of the duality. But the complexes of HPPPD with Sm（ Ⅲ ）, Tb （ Ⅲ ）, Dy （ Ⅲ ） emit weak fluorescence. The phenomenon was interpreted by electron-effect and energy-matching mechanism. Energy transfer mechanism of the luminescence in the complex was discussed.展开更多
Seven ternary Eu （m） complexes were synthesized with aromatic carboxylic acid （benzoic acid, phenylacetic acid, phenylpropionic acid and cinnamic acid） as the first ligand and 1,10-phenanthro- line or 2,2＇-dipyri...Seven ternary Eu （m） complexes were synthesized with aromatic carboxylic acid （benzoic acid, phenylacetic acid, phenylpropionic acid and cinnamic acid） as the first ligand and 1,10-phenanthro- line or 2,2＇-dipyridyl as the second ligand. The ternary Eu（ Ⅲ ） complexes were characterized by elemental analysis, IR and TG-DTG methods. In these complexes, the Eu （Ⅲ） ions are bonded to the oxygen atoms of carboxylate and the nitrogen atoms of neutral ligands. Four complexes whose second ligand is 1,10- phenanthrolin have fine thermal stability. Excitation and luminescence spectra of the tide complexes reveal that the fluorescence of the complexes in which 1,10- phenanthrolin as the second ligand are more intensive than those complexes in which 2, 2＇-dipyridyl as the second ligand. The order of the strongest emission peak of seven ternary complexes is： Eu（β-PPA）3phen 〉 Eu（BA）3phen 〉 Eu（PLA）3phen 〉 Eu（BA）3bipy 〉 Eu （ PEA）3bipy 〉 Eu （ CA ）3phen · H2O 〉 Eu （ CA ）3bipy （BA ： benzoic ; PEA ： phenylacetic ; β-PPA ：展开更多
A novel europium complex, bi(dibenzamide) benzoate europium(Ⅲ) (Eu-DBA-B), was synthesized. The composition and photoluminescence properties of Eu-DBA-B were investigated. The results show that the europium complex i...A novel europium complex, bi(dibenzamide) benzoate europium(Ⅲ) (Eu-DBA-B), was synthesized. The composition and photoluminescence properties of Eu-DBA-B were investigated. The results show that the europium complex is an electroneutral complex, and it emits very strong red luminescence from (()~5D_1→()~7F_j) (j=0, 1, 2, 3, 4) transitions.展开更多
A series of europium(III) complexes with different chain length, tris [2-m-pyridylmethanamido-5-phenyl- (1,3,4)-oxadiazole] mono [2-(4-n-alkylphenyl)-iminazole (4,5-f)-1,10-phenanthroline] Eu(III) [Eu(PMA)3Nn (n = 6, ...A series of europium(III) complexes with different chain length, tris [2-m-pyridylmethanamido-5-phenyl- (1,3,4)-oxadiazole] mono [2-(4-n-alkylphenyl)-iminazole (4,5-f)-1,10-phenanthroline] Eu(III) [Eu(PMA)3Nn (n = 6, 10, 14,18)] were synthesized. All of these amphiphilic europium(III) complexes could form stable Langmuir film at air/water interface and could be transferred onto hydrophilic quartz and mica substrates by measurement of UV spectra in which the absorbance of the LB films at about 288 nm scales showed the linearity with the number of layers deposited. In order to investigate relation between fluorescence properties and the arrangement of molecular in LB films, surface topography of monolayer films were observed by atomic force microscopy (AFM). Results showed that the emission spectra have Eu(III) characteristic peaks and strong emission strength. It is interesting that the molecular with looser arrangement in LB films has better monochromacity, which illustrated that energy might transferred more easily from ligand to Eu(III) in loosen structure films.展开更多
Terpyridine-capped poly（ethylene glycol） （PEG） was synthesized as a novel polymeric ligand and rare earth complex was prepared from Eu（NO3）3 and the telechelic macromolecules. The structure of the complex was ch...Terpyridine-capped poly（ethylene glycol） （PEG） was synthesized as a novel polymeric ligand and rare earth complex was prepared from Eu（NO3）3 and the telechelic macromolecules. The structure of the complex was characterized by 1H NMR, FT-IR, UV-vis and fluores-cence spectroscopy. Strong fluorescent emission of the complex was observed at 593 and 616 nm upon the excitation of 300 nm. The fluo-rescent emission was quenched upon addition of trace amount of diethyl chlorophosphate （DCP）. And the observed Ksv values for DCP were measured to be 0.568×10^3 and 0.89×10^3 L/mol for quenching at 593 and 616 nm, which indicated the detection limit for DCP was about 0.014 mmol/L. These results showed that the terpyridine-lanthanide complex could be an effective chemosensor with a potential application in the detection of organophosphates.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
Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synth...Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synthesized by solvent method and determined by X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group Pi. Both are binuclear molecules with an inversion center. In complex 1, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu^3＋ ion is eight-coordinated with six O atoms from five 2-TFMBA ligands and two N atoms from one 2,2′-bipy molecule. In complex 2, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu^3＋ ion is nine-coordinated with seven O atoms from five 2-TFMBA ligands and two N atoms from one 1,10-phen molecule. The two complexes both exhibited strong red fluorescence under ultraviolet light, and the ^5D0→^7Fj （j=0-4） transition emissions of Eu^3＋ ion were observed in their emission spectra.展开更多
Two ligands 2,2＇-[2,3-naphthylenebis（oxy）]-bis（N-benzyl（acetamide））（L1） and 2,2＇-[2,3-naphthylenebis （oxy）]-bis（N,N-diphenyl （acetamide））（L2） and their europium（Ill） picrate complexes were synthesi...Two ligands 2,2＇-[2,3-naphthylenebis（oxy）]-bis（N-benzyl（acetamide））（L1） and 2,2＇-[2,3-naphthylenebis （oxy）]-bis（N,N-diphenyl （acetamide））（L2） and their europium（Ill） picrate complexes were synthesized. The complexes were characterized by elemental analysis, inf,- red （IR）, thermogravimetry and differential thermal analysis （TG-DTA） and molar conductivity. Fluorescent experiments showed that the resonance level of the Eu（III） matched better to the triplet state energy level of the ligand L2 than that of the ligand L1 and the fluorescence in- tensities of the complexes were reduced with the raising coordination ability of solvent. In addition, the interactions between the complexes and DNA were studied by means of spectrometry and cyclic voltammetry. The results suggested that the complexes could bind to DNA through intercalation and the complex 1 binded to DNA more strongly than the complex 2.展开更多
基金Project supported by the Natural Science Foundation of Fujian Province(2012J01031)Educational Commission of Fujian Province(JK2012011)National Natural Science Foundation of China(61250016)
文摘The binary europium complex EuL3 （L=4-tert-butylbenzoate） and ternary europium complexes EuL3TTAo.I （TTA=2- thenoyltrifluoroacetone）, EuL3DBMo.5 （DBM=dibenzoylmethane） and EuL3pheno.5 （phen=l, 10-phenanthroline） were synthesized. The poly（methyl methacrylate） （PMMA） or copolymer of methyl methacrylate （MMA） with acrylic acid （AA） composites doped with europium complexes were prepared by radical in-situ polymerization. The influences of the europium complexes, ligands, N,N-dimethylformamide （DMF） and monomers on the luminescence properties of the doped polymers were investigated. The results showed that the fluorescence excitation bands of binary and ternary complexes were in accordance with their ultraviolet absorption bands. All the complexes and the doped polymer composites exhibited the ligand-sensitized red characteristic emission of Eu3＋ ion. The fluorescence intensity of the polymer composites increased in the sequence of EuL3/PMMA〈EuL3pheno.5/PMMA〈EuL3DBMo.5/ PMMA〈EuL3TTAo.I/PMMA. It indicated that the introduction of a small amount of I^-diketone ligand affected the optimum excita- tion wavelength and the fluorescence intensity of polymer composites. Furthermore, DMF remarkably increased the luminescence intensity and transparence of the doped polymer composites. However, introduction of acrylic acid comonomer decreased the lumi- nescence intensity of the polymer composites.
基金Project supported by the Natural Science Foundation of Beijing (2073022)
文摘A new complex of {[Eu2(2-BrBA)6(2,2’-bpy)2]2·CH3CH2OH·H2O} (2-BrBA=2-bromobenzoate; 2,2’-bpy=2,2’-bipyridine) was prepared by solvent method and characterized with X-ray single-crystal diffraction, IR spectroscopy, UV spectroscopy, and fluorescence spectroscopy. The complex crystallized in triclinic crystal system, Pī space group, with a=1.17196(4) nm, b=2.36142(9) nm, c=2.59151(9) nm, α=113.266(2)°, β=101.100(2)°, and γ=94.400(2)°. Two independent dinuclear molecules were contained in the asymmetric unit. The two molecules were similar to each other. Each Eu(Ⅲ) ion was nine-coordinated with seven oxygen atoms from five 2-BrBA ligands and two nitrogen atoms from 2,2’-bpy molecule. The carboxylate groups acted as bidentate-chelating, bidentate-bridging and chelating-bridging coordination modes. The complex adopted a distorted monocapped square-antiprism coordination geometry. Five peaks at 579, 591, 613, 652, and 697 nm appeared in the fluorescence spectrum, corresponding to 5D0→7F0, 5D0→7F1, 5D0→7F2, 5D0→7F3, and 5D0→7F4 transition emissions of the Eu(Ⅲ) ion, respectively.
基金This work was supported by the National Natural Science Foundation of China (No29992530-6) and Provincial Natural Science Foundation of Hunan (00JJY2043).
文摘Dipyrido [3, 2-a:2,3-c] phenazine moiety has been introduced as neutral ligand in europium complex. Therefore, a new europium complex with saturated emission, strong fluorescent intensity and good solubility was designed and synthesized for the first time. Its photoluminescence and UV properties were examined. The experimental results showed that this new Eu-complex could be used as red electroluminescent materials.
基金The authors gratefully thank the financial supports of 0ne Hundred Talents Project from Chinese Academy of Sciencesthe National Natural Science Foundations of China(No.20571071).
文摘A new europium（Ⅲ） complex, tris（dibertzoylmethanate）{ 1-[9-hexyl-9-carbazole]-2-（2-pyridyl）-bertzimidazole}europium（Ⅲ） [Eu（DBM）a（CPyBM）] was synthesized and used as an electron-acceptor and electron-transport layer in organic photovoltaic （PV） device. Power conversion efficiency achieved from the device was 1.04% under illumination with 365 nm UV light at 1.6 mW/cm^2. Compared with the previous reported devices based on Eu（Ⅲ） complexes, the PV performances were improved. The working mechanism of the organic PV device was discussed.
基金the Natural Science Foundation of Beijing (No. 2073022) the Young Mainstay Teachers Foundation of Beijing Municipal Universities
文摘The complex [Eu（3-IBA）3·2,2＇-bipy]2 was synthesized from 3-iodobenzoic acid （3-HIBA）, 2,2＇-bipyridine （2,2‘-bipy） and EuCl3·6H2O by hydrothermal synthesis, and its crystal structure was determined by X-ray single-crystal diffraction. It is of triclinic, space group Pi, with a = 10.958（2）, b = 12.311（3）, c = 12.556（3） A, α = 81.549（3）, β = 82.404（4）, γ = 78.348（3）°, Mr = 1049.15, V= 1631.7（6） A3, Z = 1, Dc = 2.135 g/cm^3, F（000） = 980, 2（MoKa） = 0.71073 A,μ（MoKa） = 4.804 mm^-1, the final R = 0.0329 and wR = 0.0723 for 4640 observed reflections with I 〉 2σ（I）. The Eu（Ⅲ） ion is eight-coordinated and two Eu（Ⅲ） ions are held together by four 3-iodobenzoate groups in the bidentate bridging mode. The complex was characterized by DTA-TG, IR, UV and fluorescence spectra.
基金the National Natural Science Foundation of China (20701019)the National Basic Research Program of China (973 Program, 2007CB925103)the Major State Basic Research Development Program (2006CB806104) and the EC (IST-2002-004607, OLLA)
文摘A novel dendritic europium complex containing grafted carbazole units as functional peripheries was synthesized and characterized. The Foerster energy transfer from the peripheries of carbazole units to β-diketonate as well as from the hgands to the central Eu（Ⅲ） ions in the complex was demonstrated. Under the excitation of carbazole units and β-diketonate, characteristic red emission peaks at 612 nm with four shoulders due to the Eu（Ⅲ） ion transition of 5^D0→7^FJ （J=0-4） were observed for the complex.
基金Project supported by the National Natural Science Foundation of China.China(21861017,41867053)the Key Project of Natural Science Foundation of Jiangxi Province,China(20192ACBL20011).
文摘A new europium complex Eu(tta)_(3)Li(la)based on 1,10-phenanthroline derivative(Li=(2-(3,5-dimethoxyphenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline),tta=2-thenoyItrifluoroacetone)was designed and synthesized.Its structure was characterized by^(1)H and^(13)C NMR,elemental analysis,UV-vis,fluorescence spectra and single crystal X-ray diffraction.The crystal of the complex la belongs to monoclinic system with the space group P2_(1/n).The europium complex la in the solid and in the solution displays the typical emission of Eu(III)ion centered at 612 nm as a result of the electric dipole transition(^(5)D_(0)-►^(7)F_(2)).It exhibits high quantum yield(20.42%),long lifetime(0.29 ms)and good CIE color coordinate(0.67,0.33)in solid.In addition,the complex shows high sensitivity and selectivity towards Al^(3+)and Zn^(2+)in methanol solution which can be attributed to the Al^(3+)/Zn^(2+)cation instead of Eu^(3+)in the complex la.The LODs for Al^(3+)and Zn^(2+)were calculated to be 5.880×10^(-7)and 7.678×10^(-8)mol/L,respectively.Besides,the additions of Al^(3+)and Zn^(2+)express remarkable color changes from red to bright blue and ivory that can be clearly observed by the naked eye respectively.
文摘A novel organic ligand, 6 (ortho methyl anilino carbonyl) 2 pyridine carboxylic acid (H o MAP), and the corresponding europium complex, tris(6 (ortho methyl anilino carbonyl) 2 pyridine carboxylato) europium (Eu o MAP) were designed and synthesized. The results show that solid Eu o MAP is a conjugated complex, emitting strong red fluorescence dominantly due to a ligand sensitizd luminescence mechanism. The lifetimes of 5D 0 of Eu 3+ in the complex were examined using time-resolved spectroscopic analysis, and the lifetime values were (1.50±0.01) ms for solid Eu(o MAP) 3 and (1.10±0.01) ms for 1.0×10 -5 mol·L -1 Eu(o MAP) 3 ethanol solution, respectively. Thermogravimetric analysis shows that the europium complex has good thermal stability.
基金supported by the Science and Technology Program, Beijing Municipal Education Commission (09224010010)
文摘A new chain europium complex [Eu(2,3-DFBA)3·(H2O)2]n(2,3-DFBA=2,3-difluorobenzoate) was synthesized by solvent method.X-ray single-crystal diffraction analysis revealed that Eu3+ ions were linked through 2,3-DFBA groups via alternate bidentate-bridging and tridentate chelating-bridging coordination modes to form a one-dimensional(1-D) polymeric chain.Each Eu3+ ion is eight-coordinated by six O atoms of five 2,3-DFBA ligands and two water molecules.The abundant hydrogen bonds between chains resulted in a two...
基金Project supported by the Young Mainstay Teachers Foundation of Beijing Municipal Universities
文摘A new complex Eu2（PA）6（phen）2 was prepared with hydrothermal reaction using EuCl3.6H2O, phenylmalonic acid （H2phma）, and 1, 10-phenanthroline （phen）, where PA was the decarboxylated product of HEphma, phenylacetate. The crystal structure of the title complex was determined with the X-ray diffraction. The title complex was a binuclear molecule with an inversion center. Each Eu^3＋ ion was nine-coordinated with two nitrogen atoms from one phen molecule and seven oxygen atoms from five PA ligands. The carboxylic groups were bonded to the Eu^3＋ ion in three modes, the chelating bidentate, the bridging bidentate, and the bridging-chelating tridentate. The complex emits intense red fluorescence under ultraviolet light. The luminescence peaks correspond to the characteristic emission 5D0→7FJ （J=0-4） transitions of the Eu^3＋ ion.
基金Supported by the National Natural Science Foundation of China, St. Michael's College the National Science Foundation, R11-8610679(Vermont EPSCOR), U. S. A.
文摘A series of euroPium(Ⅱ)eomPlexes with earboxylie aeids andl,10-Phenantl飞ro-line:Eu(L):·pllen·jHoO,wl:ereL-formate,3-hydroxy-4-metlloxybenzoate,4一metl、oxybenzoate,4一ehloroPhenoxyaeetate,and diPI、enylaeetate,were synthesizedand el、araeterized by elemental analysis,UV sPeetrum,IR speetrum and melting point.IR da亡a eonfirmed tllat euroPium 15 eoordinated wirh 0 donor atoms in earboxy!ie aeidand N donor atoms inl,10一phenanthroline.A strong ligand一loealized absorption at270 nm!ed to a series of meta!一eentered emission bands between 580 and 710 nm as-signedto ~5D_0-7F_(0.1.2.3.)
文摘Tris (thenoyltrifluoroacetonato) mono(9-octadecylamino-4,5-diazafluorene) europium (III) was synthesized. Stable floating monolayer on pure water subphase (18 degrees C, pH 5.6) was obtained with a collapse pressure of 40 mN/m and a zero-pressure area of 0.495 nm(2) molecule(-1). The monolayers can be transferred onto hydrophilically treated substrates of quartz, calcium fluoride at a surface pressure of 25 mN/m with a transfer ratio of ca. unity. The films were characterized by UV, IR and fluorescent spectroscopy.
文摘Using 2＇-Hydroxyacetophenone and as the raw material, 1-（ 2-Hydroxyphenyl ）-3-Phenyl-1, 3- Propanedione （HPPPD） was synthesized by esterification reaction and Fries rearrangement reaction. And the complexes of HPPPD with europium were also synthesized. The compounds were characterized by IR, thermo-gravimetric analysis and ^1H-NMR. The effects of phenolic hydroxyl on the luminescence properties of complexes were studied. The results show that the complexes emit strong red fluorescence and the fluorescence intensity of the ternary complex is better than that of the duality. But the complexes of HPPPD with Sm（ Ⅲ ）, Tb （ Ⅲ ）, Dy （ Ⅲ ） emit weak fluorescence. The phenomenon was interpreted by electron-effect and energy-matching mechanism. Energy transfer mechanism of the luminescence in the complex was discussed.
文摘Seven ternary Eu （m） complexes were synthesized with aromatic carboxylic acid （benzoic acid, phenylacetic acid, phenylpropionic acid and cinnamic acid） as the first ligand and 1,10-phenanthro- line or 2,2＇-dipyridyl as the second ligand. The ternary Eu（ Ⅲ ） complexes were characterized by elemental analysis, IR and TG-DTG methods. In these complexes, the Eu （Ⅲ） ions are bonded to the oxygen atoms of carboxylate and the nitrogen atoms of neutral ligands. Four complexes whose second ligand is 1,10- phenanthrolin have fine thermal stability. Excitation and luminescence spectra of the tide complexes reveal that the fluorescence of the complexes in which 1,10- phenanthrolin as the second ligand are more intensive than those complexes in which 2, 2＇-dipyridyl as the second ligand. The order of the strongest emission peak of seven ternary complexes is： Eu（β-PPA）3phen 〉 Eu（BA）3phen 〉 Eu（PLA）3phen 〉 Eu（BA）3bipy 〉 Eu （ PEA）3bipy 〉 Eu （ CA ）3phen · H2O 〉 Eu （ CA ）3bipy （BA ： benzoic ; PEA ： phenylacetic ; β-PPA ：
文摘A novel europium complex, bi(dibenzamide) benzoate europium(Ⅲ) (Eu-DBA-B), was synthesized. The composition and photoluminescence properties of Eu-DBA-B were investigated. The results show that the europium complex is an electroneutral complex, and it emits very strong red luminescence from (()~5D_1→()~7F_j) (j=0, 1, 2, 3, 4) transitions.
文摘A series of europium(III) complexes with different chain length, tris [2-m-pyridylmethanamido-5-phenyl- (1,3,4)-oxadiazole] mono [2-(4-n-alkylphenyl)-iminazole (4,5-f)-1,10-phenanthroline] Eu(III) [Eu(PMA)3Nn (n = 6, 10, 14,18)] were synthesized. All of these amphiphilic europium(III) complexes could form stable Langmuir film at air/water interface and could be transferred onto hydrophilic quartz and mica substrates by measurement of UV spectra in which the absorbance of the LB films at about 288 nm scales showed the linearity with the number of layers deposited. In order to investigate relation between fluorescence properties and the arrangement of molecular in LB films, surface topography of monolayer films were observed by atomic force microscopy (AFM). Results showed that the emission spectra have Eu(III) characteristic peaks and strong emission strength. It is interesting that the molecular with looser arrangement in LB films has better monochromacity, which illustrated that energy might transferred more easily from ligand to Eu(III) in loosen structure films.
基金Project supported by Research Foundation of the General Armament Department (2008CD012)
文摘Terpyridine-capped poly（ethylene glycol） （PEG） was synthesized as a novel polymeric ligand and rare earth complex was prepared from Eu（NO3）3 and the telechelic macromolecules. The structure of the complex was characterized by 1H NMR, FT-IR, UV-vis and fluores-cence spectroscopy. Strong fluorescent emission of the complex was observed at 593 and 616 nm upon the excitation of 300 nm. The fluo-rescent emission was quenched upon addition of trace amount of diethyl chlorophosphate （DCP）. And the observed Ksv values for DCP were measured to be 0.568×10^3 and 0.89×10^3 L/mol for quenching at 593 and 616 nm, which indicated the detection limit for DCP was about 0.014 mmol/L. These results showed that the terpyridine-lanthanide complex could be an effective chemosensor with a potential application in the detection of organophosphates.
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supported by the Natural Science Foundation of Beijing (2073022)
文摘Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synthesized by solvent method and determined by X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group Pi. Both are binuclear molecules with an inversion center. In complex 1, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu^3＋ ion is eight-coordinated with six O atoms from five 2-TFMBA ligands and two N atoms from one 2,2′-bipy molecule. In complex 2, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu^3＋ ion is nine-coordinated with seven O atoms from five 2-TFMBA ligands and two N atoms from one 1,10-phen molecule. The two complexes both exhibited strong red fluorescence under ultraviolet light, and the ^5D0→^7Fj （j=0-4） transition emissions of Eu^3＋ ion were observed in their emission spectra.
基金Project supported by National Natural Science Foundation of China (20962016)the Key Research Foundation of Education Ministry of China (208159)
文摘Two ligands 2,2＇-[2,3-naphthylenebis（oxy）]-bis（N-benzyl（acetamide））（L1） and 2,2＇-[2,3-naphthylenebis （oxy）]-bis（N,N-diphenyl （acetamide））（L2） and their europium（Ill） picrate complexes were synthesized. The complexes were characterized by elemental analysis, inf,- red （IR）, thermogravimetry and differential thermal analysis （TG-DTA） and molar conductivity. Fluorescent experiments showed that the resonance level of the Eu（III） matched better to the triplet state energy level of the ligand L2 than that of the ligand L1 and the fluorescence in- tensities of the complexes were reduced with the raising coordination ability of solvent. In addition, the interactions between the complexes and DNA were studied by means of spectrometry and cyclic voltammetry. The results suggested that the complexes could bind to DNA through intercalation and the complex 1 binded to DNA more strongly than the complex 2.
