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
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
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
The research on electroluminescence based on europium(III) complexes has come to an important phase. This article reviewed the progresses in photoluminescence and electrohiminescence of Eu(III) complexes in recent...The research on electroluminescence based on europium(III) complexes has come to an important phase. This article reviewed the progresses in photoluminescence and electrohiminescence of Eu(III) complexes in recent years from the views of the design of Eu(III) complexes and optimization of device structures, and discussed some important factors influencing electroluminescence performance. The problems existing in the practical application such as the volatility and thermal stability of Eu(III) complexes in this area were discussed, and the possible corresponding solutions were briefly prospected.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 luminescent rare earth(RE)complex based multifunctional nanocomposites offer new potential applications of multimodal imaging(magnetic resonance imaging(MRI),fluorescent bioimaging,etc.)that can be associated with...The luminescent rare earth(RE)complex based multifunctional nanocomposites offer new potential applications of multimodal imaging(magnetic resonance imaging(MRI),fluorescent bioimaging,etc.)that can be associated with therapeutic activities.In this study,we report some results obtained with novel multifunctional Fe3O4/Si-amine/Eu(NTA)3 nanocomposites that are composed of europium(Ⅲ)complex with 1-(2-naphthoyl)-3,3,3-trifluoroacetone ligands(NTA)(Eu(NTA)3)and superparamagnetic Fe3O4 nanoparticles.These nanocomposites were functionalized with an amine group for biomedicine application.The multifunctional Fe3O4/Si-amine/Eu(NTA)3 nanocomposites exhibit both good magnetic behavior of Fe3O4 nanoparticles as a core and strong fluorescent property of europium(Ⅲ)complex.Their characterizations were analyzed by XRD,SEM,EDX and FTIR spectra.The optical properties were studied in detail by UV-VIS spectra and luminescent emission spectra.The magnetic property was estimated by VMS.The effect of concentrations of luminescent Eu(NTA)3 complex on luminescent and magnetic properties is discussed.展开更多
A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.95...A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.展开更多
A novel binuclear Eu(Ⅲ) complex [Eu2(dpa dioxide)2(NO3)4(bpdioxide)-(EtOH)] (dpa dioxide = di-2-pyridylamine N,N'-dioxide, bpdioxide = 2,2'-bipyridine N,N'-dioxide) has been synthesized and it exhibits...A novel binuclear Eu(Ⅲ) complex [Eu2(dpa dioxide)2(NO3)4(bpdioxide)-(EtOH)] (dpa dioxide = di-2-pyridylamine N,N'-dioxide, bpdioxide = 2,2'-bipyridine N,N'-dioxide) has been synthesized and it exhibits strong and sharp fluorescent emission at 614 nm under UV radiation of 245 nm at room temperature. X-ray structural determination indicates two independent Eu(Ⅲ) ions in the structure with different EuO8N and EuOgN environments. The compound crystallizes in the triclinic system, space group P1, with a = 10.8089(7), b = 11.4670(8), c = 17.1440(12) A, α = 92.834(2), β = 93.854(3), γ = 95.433(2)°, Z = 2, Dc = 1.876 g/cm3, V= 2107.3(2) A3, F(000) = 1168.0, the final R = 0.032 and wR = 0.086 for 6331 observed reflections with I 〉 2σ(I).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 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
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
The crystal structure of europium tri(dibenzoylmethanate) complex with 2.2'-bipyridyl,C70 H57 N2 O8 Eu, has been determined by X-ray diffraction. The complex crystallizes in the triclinic space group P1. The cell ...The crystal structure of europium tri(dibenzoylmethanate) complex with 2.2'-bipyridyl,C70 H57 N2 O8 Eu, has been determined by X-ray diffraction. The complex crystallizes in the triclinic space group P1. The cell dimensions are a=1.3375(1) nm.b=1.8591(2) nm, c=1.1339(3) nm,α= 95.89(9) °,β=93.36(1)°,γ=85.48(1)° and Z=2. The total number of 5413 independent reflections with I>3σ(I) were used for the structure determination. The final calculated R value is 0.039. The central europium ion is octa-coordinated by six oxygen atoms and two nitrogen atoms forming a distorted square antipnsm (SAP) with the local symmetry C1. Using the Eu3+ ion as a luminescence probe. the high resolution excitation and emission spectra measured at 77 K indicate only one Eu3+ site existing in the complex. The emission spectra of 5D0→7Fj transition display the symmetry of the Eu3+ site is C1.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
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
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 new europium(Ⅲ)complex Eu_(2)(C_(15)H_(11)O_(3))_(6)(C_(12)H_(8)N_(2))_(2)has been synthesized with 2-(4-Methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:mon...A new europium(Ⅲ)complex Eu_(2)(C_(15)H_(11)O_(3))_(6)(C_(12)H_(8)N_(2))_(2)has been synthesized with 2-(4-Methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2_(1/n),a=15.1238(5),b=13.5928(4),c=22.9840(7)A,β=104.132(3)o,V=4582.0(2)A3,Dc=1.522 g/cm^(3),Z=4,μ(Mo Kα)=1.433 mm^(-1),F(000)=2128,the final R=0.0447 and wR=0.0826.The Eu(Ⅲ)ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu^(3+):5 D0→7 F1(594 nm)and 5 D0→7 F2(617 nm).The complex is an antiferromagnetism system in the range of 150~300 K.Also reported in the paper is the thermal stability property of the title complex.展开更多
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 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 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supported by the National Basic Research Program (2006CB601103)the National Natural Science Foundation of China (20221101, 20423005, 20471004, 90401028, 50372002, 20671006)
文摘The research on electroluminescence based on europium(III) complexes has come to an important phase. This article reviewed the progresses in photoluminescence and electrohiminescence of Eu(III) complexes in recent years from the views of the design of Eu(III) complexes and optimization of device structures, and discussed some important factors influencing electroluminescence performance. The problems existing in the practical application such as the volatility and thermal stability of Eu(III) complexes in this area were discussed, and the possible corresponding solutions were briefly prospected.
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Project supported by Vietnam Academy of Science and Technology(VAST03.03/18-19)
文摘The luminescent rare earth(RE)complex based multifunctional nanocomposites offer new potential applications of multimodal imaging(magnetic resonance imaging(MRI),fluorescent bioimaging,etc.)that can be associated with therapeutic activities.In this study,we report some results obtained with novel multifunctional Fe3O4/Si-amine/Eu(NTA)3 nanocomposites that are composed of europium(Ⅲ)complex with 1-(2-naphthoyl)-3,3,3-trifluoroacetone ligands(NTA)(Eu(NTA)3)and superparamagnetic Fe3O4 nanoparticles.These nanocomposites were functionalized with an amine group for biomedicine application.The multifunctional Fe3O4/Si-amine/Eu(NTA)3 nanocomposites exhibit both good magnetic behavior of Fe3O4 nanoparticles as a core and strong fluorescent property of europium(Ⅲ)complex.Their characterizations were analyzed by XRD,SEM,EDX and FTIR spectra.The optical properties were studied in detail by UV-VIS spectra and luminescent emission spectra.The magnetic property was estimated by VMS.The effect of concentrations of luminescent Eu(NTA)3 complex on luminescent and magnetic properties is discussed.
基金supported by the Construct Program of the Key Discipline in Hunan Province
文摘A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.
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 binuclear Eu(Ⅲ) complex [Eu2(dpa dioxide)2(NO3)4(bpdioxide)-(EtOH)] (dpa dioxide = di-2-pyridylamine N,N'-dioxide, bpdioxide = 2,2'-bipyridine N,N'-dioxide) has been synthesized and it exhibits strong and sharp fluorescent emission at 614 nm under UV radiation of 245 nm at room temperature. X-ray structural determination indicates two independent Eu(Ⅲ) ions in the structure with different EuO8N and EuOgN environments. The compound crystallizes in the triclinic system, space group P1, with a = 10.8089(7), b = 11.4670(8), c = 17.1440(12) A, α = 92.834(2), β = 93.854(3), γ = 95.433(2)°, Z = 2, Dc = 1.876 g/cm3, V= 2107.3(2) A3, F(000) = 1168.0, the final R = 0.032 and wR = 0.086 for 6331 observed reflections with I 〉 2σ(I).
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.
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.
文摘The crystal structure of europium tri(dibenzoylmethanate) complex with 2.2'-bipyridyl,C70 H57 N2 O8 Eu, has been determined by X-ray diffraction. The complex crystallizes in the triclinic space group P1. The cell dimensions are a=1.3375(1) nm.b=1.8591(2) nm, c=1.1339(3) nm,α= 95.89(9) °,β=93.36(1)°,γ=85.48(1)° and Z=2. The total number of 5413 independent reflections with I>3σ(I) were used for the structure determination. The final calculated R value is 0.039. The central europium ion is octa-coordinated by six oxygen atoms and two nitrogen atoms forming a distorted square antipnsm (SAP) with the local symmetry C1. Using the Eu3+ ion as a luminescence probe. the high resolution excitation and emission spectra measured at 77 K indicate only one Eu3+ site existing in the complex. The emission spectra of 5D0→7Fj transition display the symmetry of the Eu3+ site is C1.
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Supported by The State Key Program of Fundam ental Research( G19980 613 0 8) ,National Natural Science Foundationof China( Nos.2 99710 0 5 ,2 0 0 2 3 0 0 5 ,2 0 0 710 0 4) ,and Scientific Research Foundation for the Returned Overseas ChineseScholars( S
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.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.
基金supported by the cooperative project of Hengyang Normal University with Hengyang Yile New Materials Co.,Ltd.(No.HXKJ201905)
文摘A new europium(Ⅲ)complex Eu_(2)(C_(15)H_(11)O_(3))_(6)(C_(12)H_(8)N_(2))_(2)has been synthesized with 2-(4-Methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2_(1/n),a=15.1238(5),b=13.5928(4),c=22.9840(7)A,β=104.132(3)o,V=4582.0(2)A3,Dc=1.522 g/cm^(3),Z=4,μ(Mo Kα)=1.433 mm^(-1),F(000)=2128,the final R=0.0447 and wR=0.0826.The Eu(Ⅲ)ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu^(3+):5 D0→7 F1(594 nm)and 5 D0→7 F2(617 nm).The complex is an antiferromagnetism system in the range of 150~300 K.Also reported in the paper is the thermal stability property of the title complex.