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1.
Luminescence properties of lanthanide(III) ions (Ln = Nd, Sm, Eu, Gd, Tb, Dy and Tm) were investigated by measuring the excitation and emission spectra, and emission lifetimes in H2O and D2O solutions of 3 moll?1 K2CO3, where anionic tetra-carbonate complexes, [Ln(CO3)4]5- were the predominant species.

Electronic transitions of the carbonato complex corresponding to both the excitation and emission spectra were assigned from the energy level diagrams of Ln(III) and compared with those of the aqua ion. Enhancement of emission intensity of the complex was observed at particular excitation transitions of Eu(III), Gd(III) and Tb(III), and at particular emission transitions of Sm(III), Eu(III), Dy(III) and Tm(III). The enhancement at the emission transition was estimated quantitatively as a branching ratio from the lowest emitting state of Ln(III), and discussed in terms of hypersensitivity.

Emission lifetimes of the carbonato complexes were all longer than those of aqua ions in H2O solution, while the lifetimes of the complexes for Eu(III) and Tb(III) shorter than those in D2O solution. The difference in non-radiative decay constants for the excited complex in H2O and D2O solutions was found to be proportional to an exponential of the energy gap of Ln(III). The lifetime ratio between the H2O and D2O solutions showed the order of Sm > Dy > Eu > Tb, corresponding to the opposite order of the energy gap. These were discussed in terms of an energy gap law, i.e. a relationship between the energy gap of Ln(III) and vibration energies of the ligand or water molecules.  相似文献   

2.
A novel Aryl amide ligand H2L and its eight complexes, [LnH2L(NO3)2·H2O]NO3 [Ln=Sm(III), Er(III), Tb(III), Dy(III), La(III), Gd(III), Nd(III), and Pr(III)], are presented. The ligand and complexes were synthesized and characterized based on elemental analyses, molar conductance, IR, 1H and 13C-NMR, UV–VIS., and TGA studies. The conductivity data show a 1:1 electrolytic nature with a general formula [LnH2L(NO3)2·2H2O]NO3 The IR spectra reveal coordination of the ligand through the azomethine nitrogen and the phenolic hydroxyl of the ligand to the lanthanide ion. The coordinated nitrate ions behave in a bidentate fashion. The thermal decomposition studies indicate the presence of two water molecules in the inner coordination sphere. Under the excitation at 319 nm, the luminescence emission properties for Sm, Tb, and Dy complexes are observed. These observations show that the ligand favors energy transfers to the emitting energy level of these lanthanide ions. Furthermore, the antioxidant activity of the ligand and its Ln(III) complexes was determined by DPPH radical scavenging method, which indicates that the Ln(III) complexes exhibit more effective antioxidant activity than the ligand alone.  相似文献   

3.
A new Eu(III)/Tb(III) binuclear coordination compound with red and yellow emissions in solution and solid state, respectively, has been prepared. The lanthanide (Ln) ions are coordinated to crown ethers (C) and bridged by a dipyridyl (dipy) ligand. Ln/C and Ln/C/dipy complexes were also synthesized as precursors for the bimetallic compounds. The homo- and heterobimetallic Ln(III) complexes were characterized by elemental analysis as well as infra-red, absorption (UV-visible) and emission spectroscopies. The heterobimetallic complex geometry was predicted using the Sparkle/AM1 model and suggested to a chemical environment of very low symmetry around the lanthanide ions (C1), in agreement with the luminescence spectrum. The Eu(III) and Tb(III) complexes display intense red and green emissions, respectively, in the solid state at room temperature.  相似文献   

4.
The mono(pyridine-N-oxide) analog of the H4dota macrocylic ligand, H3do3a-pyNO, is capable of forming thermodynamically stable and kinetically inert Ln(III) complexes. Its Eu(III) and Tb(III) complexes display a strong long-lived fluorescence as a result of the antenna effect of the pyridine-N-oxide fluorophore in the reagent. It is shown that H3do3a-pyNO can be used as a fluorogenic reagent for the determination of Eu(III) and Tb(III) at pH 6.5 and cL=1 mM. At an excitation wavelength of 286 nm, the emission maxima are 615 nm (Eu(III)-complex), and 547 nm (Tb(III)complex). Detection limits are at concentrations around 1.0 μM and linearity of the method spans over 2 orders of magnitude. The method was applied to artificial and real samples (spiked mineral waters, extracts from cathode ray tube luminophore dust) and gave satisfactory results. The method is simple, rapid, and hardly interfered by other metal ions.  相似文献   

5.
The intensity I lum and lifetime τlum of the luminescence of complexes of Eu(III) and Tb(III) ions with β-diketones and o-phenanthroline in water-ethanol solutions of these ligands have been analyzed as functions of the concentrations of ligand, luminescing lanthanide ions, and added ions causing columinescence and of the solvent deuteration. It is shown that the formation of nanostructures from Ln complexes and their coarsening leads to an increase in τlum of Eu(III) and Tb(III) and that this increase is due to the suppression of both photochemical deexcitation of these ions and transfer of their electronic excitation energy to OH vibrations of water molecules. The disappearance of the dependence of I lum of Eu(III) on deuteration of water-ethanol solutions of n-methoxybenzoyltrifluoracetone + o-phenanthroline caused by adding Gd(III) ions is explained by the shift of the equilibrium of formation of complexes of Ln chelates to neutral hydrophoblic forms corresponding to the formation of nanostructures of these chelates in the solution. The differences in effect of La(III) and Gd(III) ions on I lum and τlum of Eu(III) and Tb(III) complexes are explained. It is shown that the widely discussed effect of columinescence not only results from the energy migration in mixed structures of Eu or Tb complexes and Gd complexes but is also due to a large extent to the decrease in τlum of Eu(III) or Tb(III) caused by their incorporation into nanostructures.  相似文献   

6.
This work reports on the synthesis, crystallographic determination and spectroscopic characterization of gadolinium(III), terbium(III) and europium(III) 3-mercaptopropionate complexes, aqua-tris(3-mercaptopropionate)lanthanide(III) - [Ln(mpa)3(H2O)]. The Judd-Ofelt intensity parameters were experimentally determined from emission spectrum of the [Eu(mpa)3(H2O)]complex and they were also calculated from crystallographic data. The complexes are coordination polymers, where the units of each complex are linked together by carboxylate groups leading to an unidimensional and parallel chains that by chemical interactions form a tridimensional framework. The emission spectrum profile of the [Eu(mpa)3(H2O)] complex is discussed based on point symmetry of the europium(III) ion, that explains the bands splitting observed in its emission spectrum. Photoluminescent analysis of the [Gd(mpa)3(H2O)] complex show no efficient ligand excitation but an intense charge transfer band. The excitation spectra of the [Eu(mpa)3(H2O)] and [Tb(mpa)3(H2O)] complexes do not show evidence of energy transfer from the ligand to the excited levels of these trivalent ions. Therefore the emission bands are originated only by direct f-f intraconfigurational excitation of the lantanide(III) ions.  相似文献   

7.
The formation of nanostructures that consist of complexes of β-diketones with 1,10-phenanthroline and involve dyes of the polymethine, triphenylmethane, oxazine, and xanthene series is observed in aqueous solutions. It is found that nanostructures of complexes of Ln(III) ions and dyes are reliably observed at concentrations of Ln complexes from 0.5 to 5 μM and at dye concentrations above 5 nM. Nanostructures of complexes Eu(MBTA)3phen, Eu(NTA)3phen, Eu(PTA)3phen, Tb(PTA)3phen, Gd(MBTA)3phen, and Lu(MBTA)3phen with dyes are studied, where MBTA is n-methoxybenzoyltrifluoroacetone, NTA is naphthoyltrifluoroacetone, PTA is pivaloyltrifluoroacetone, and phen is 1,10-phenanthroline. It is shown that nanostructures formed can contain dye molecules not only inside a nanostructure of Ln complexes but also on its outer shell. It is proved that, at a dye concentration in the solution of the order of nanomole or higher, the formation of mixed nanostructures of Eu complexes and dyes whose S 1 level is below the 5 D 0 level of Eu(III) leads to the quenching of the luminescence of Eu(III) and gives rise to the sensitized luminescence of dyes. The energy transfer efficiency from Eu(III) ions to dye molecules is determined by the ability of these molecules to incorporate into nanostructures of Eu complexes. The effect of the formation of nanostructures on the shape and position of the spectra of luminescence and absorption of dyes is studied. Comparison of the sensitized luminescence intensities of Nile blue in structures of Eu, Lu, and Gd complexes shows that the greater part of the excitation energy of Eu complexes is transferred directly from ions to dye molecules according to the inductive-resonance energy transfer mechanism rather than by means of energy migration over singlet levels of organic ligands in complexes of a nanostructure.  相似文献   

8.
Li WX  Guo L  Chen LJ  Shi XY 《Journal of fluorescence》2008,18(6):1043-1049
A ligand with two carbonyl groups and one sulfinyl group has been synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, 1H NMR and UV spectra. The results indicated that the composition of these complexes is REL5(ClO4)3·3H2O (RE = La(III), Pr(III), Eu(III), Tb(III), Yb(III), L = C6H5COCH2SOCH2COC6H5). The fluorescent spectra illustrate that both the Tb (III) and Eu (III) complexes display characteristic metal-centered fluorescence in solid state, indicating the ligand favors energy transfer to the excitation state energy level of them. However, the Tb (III) complex displays more effective luminescence than the Eu (III) complex, which is attributed to especial effectively in transferring energy from the average triplet energy level of the ligands (T) onto the excited state (5D4) of Tb (III) than that (5D0) of Eu (III), showing a good antenna effect for Tb(III) luminescence. The phosphorescence spectra and the relationship between fluorescence lifetimes and fluorescence intensities were also discussed.  相似文献   

9.
6-Hydroxy chromone-3-carbaldehyde-(4′-hydroxy) benzoyl hydrazone (L) and its Ln (III) complexes, [Ln = La, Nd, Eu and Tb] have been prepared and characterized on the basis of elemental analyses, molar conductivities, mass spectra, 1H NMR, thermogravimety/differential thermal analysis (TG-DTA), UV-vis spectra, fluorescence spectra and IR spectra. The formula of the complex is [Ln L·(NO3)2]·NO3. Spectrometric titration, ethidium bromide displacement experiments and viscosity measurements indicate that Eu (III) complex bind with calf-thymus DNA, presumably via an intercalation mechanism. The intrinsic binding constant of Eu (III) with DNA was 2.48 × 105 M−1 through fluorescence titration data.  相似文献   

10.
Two novel ternary rare earth complexes LnL5L′(ClO4)32H2O (Ln=Eu(III), Tb(III); L=bis(benzoylmethyl) sulfoxide, L′=phen) were synthesized and characterized by elemental analysis, coordination titration analysis, molar conductivity, IR, TG-DSC,1H NMR and UV spectra. The fluorescence spectra illustrated that both the Eu(III) and Tb(III) ternary complexes displayed strong characteristic metal-centered fluorescence in solid state. After the introduction of the second ligand phen group, the relative emission intensities and fluorescence lifetimes of the ternary complex EuL5L′(ClO4)32H2O (L=C6H5COCH2SOCH2COC6H5, L′=phen) enhanced more obviously than that of the binary complex EuL5(ClO4)33H2O. This indicated that the presence of both organic ligands bis(benzoylmethyl) sulfoxide and the second ligand phen could sensitize fluorescence intensities of Eu(III) ions, and the introduction of phen group was resulted in the enhancement of the fluorescence properties of the Eu(III) ternary rare earth complexes. The phosphorescence spectra are also discussed.  相似文献   

11.
We studied sensitization of Eu(III) and Tb(III) ions by molecules of 1,10-phenanthroline and 2,2-bipyridil in D2O and d 6-ethanol and the influence of Nd(III), Pr(III), Sm(III), Gd(III), and Ho(III) ions on the luminescence intensity I lum and lifetime τlum of Eu(III) and Tb(III) in solutions. The stability constants of complexes of Eu(III) and Gd(III) with 2,2′-bipyridil are measured by spectrophotometric and luminescence methods. It is shown that luminescence of Eu(III) is quenched by Gd(III) ions at the ion concentration equal to 10?2–10?1 M, which is caused by competing between these ions for a sensitizer. At the concentration of Ln(III) ions equal to 10?6?10?3 M, the sensitized luminescence of Eu(III) and Tb(III) was quenched and τlum decreased in the presence of Nd(III) ions, whereas in the presence of Gd(III) the luminescence intensity increased. It is proved that a bridge that connects the two ions upon energy transfer is formed by hydroxyl groups. The intensity of luminescence of Eu(III) and Tb(III) in aqueous solutions and its lifetime decreased in the presence of hydroxyl groups, while upon addition of Gd(III) to these solutions these quantities were restored. We also found that the addition of Gd(III) to deoxygenated ethanol solutions of 2,2′-bipyridil and Eu(III) slows down photochemical and thermal reactions between bipyridil and Eu(III), resulting in the increase in the luminescence intensity of Eu(III).  相似文献   

12.
This paper reports the structural, magnetic and optical properties of three series of lanthanide complexes [Ln(radical)4](ClO4)3, [Ln(radical)2(NO3)3] and [Ln(radical)(hfac)3] (Ln=Gd(III), La(III) or Eu(III)) with nitronyl or imino nitroxide radicals.The magnetic properties of the gadolinium complexes were studied. Along the series, most gadolinium(III) complexes exhibit antiferromagnetic GdIII-radical interaction. These results are discussed.The full absorption and luminescence spectra of some lanthanide complexes and their uncoordinated free radical ligands were measured. The rich vibronic structure in luminescence and absorption spectra indicates that several excited states define the absorption spectra between 400 and 800 nm. Qualitative trends can be established between magnetic ground state properties and the energies and vibronic structure of the title compounds.  相似文献   

13.
Six novel complexes of lanthanide nitrates (Ln = La, Sm, Eu, Gd, Tb, Dy) with a amide type ligand, N-methyl-N-phenyl-2-(quinolin-8-yloxy)acetamide (L) have been prepared and characterized by elemental analysis, conductivity measurements, IR and 1H NMR spectra. The fluorescence properties of the complexes and the triplet state energy of the ligand were studied in detail. The result indicates that, the triplet state energy level of the ligand matches better to the resonance level of Eu(III) than Tb(III). In addition, the fluorescence intensities of the Eu(III) complex in different solutions(tetrahydrofuran, acetone and acetonitrile) are stronger than that in solid state. This is probably due to the solvate effect and the stoichiometry change of ligand with Eu(III) ion in solutions.  相似文献   

14.
Rare-earth complexes [(TbxTmy)L5(ClO4)2](ClO4)·3H2O(x:y=1.000:0.000, 0.999:0.001, 0.995:0.005, 0.990:0.010, 0.950:0.050, 0.900:0.100, 0.800:0.200, 0.700:0.300; L=C6H5COCH2SOCH2COC6H5) were synthesized and characterized with elemental analysis, infrared spectra (IR) and 1H NMR. The photophysical properties of these complexes were studied in detail with ultraviolet absorption spectra, fluorescent spectra and lifetimes. The fluorescence spectra and decay curves of complexes indicated that the fluorescence emission intensity was enhanced and the fluorescence lifetime was prolonged by Tm (III), which may be due to the intra-molecular energy transfer between inert rare-earth ions and active rare-earth ions. The complexes showed the best properties when the mole ratio of Tb (III) to Tm (III) is 0.995:0.005. The intensity of fluorescence can be increased to 208%. Additionally, the energy-transfer mechanisms between the ligand and the central Tb (III) ions were discussed.  相似文献   

15.
The reaction of Ln(ClO4)3· nH2O with triphenylphosphine oxide (TPPO) in methanol has led to the formation of [Ln(ClO4)2(tppo)4]ClO4·MeOH (Ln = Nd, Eu, Gd, Dy, Yb), in which the perchlorate anion acts as a symmetric bidentate. The emission spectra of Eu(III)-TPPO complexes, showing enhancement in the intensity due to the phenyl group, indicate an isotropic electron distribution for the nitrato complex [Eu(NO3)3(tppo)2(EtOH)]. 151Eu and 155Gd M?ssbauer spectra of the TPPO complexes also lead to the same conclusion.  相似文献   

16.
Uninuclear europium (Eu), as well as binuclear Eu and terbium (Tb), complexes were synthesized using acrylic acid (AA) as the first ligand and 1,10-phenanthroline (Phen) as the second ligand. The relative weight ratio of the europium (III) (Eu3+) to terbium (III) (Tb3+) ions of the binuclear complex was 1:1 as determined via energy dispersive X-ray analysis. The structures of the Eu(AA)3Phen and Eu0.5Tb0.5(AA)3Phen complexes were characterized by Fourier transform infrared spectroscopy. A series of tri-cellulose acetate (TCA)/ the Eu(AA)3Phen and TCA/Eu0.5Tb0.5(AA)3Phen composites were prepared by solution blending, and their luminescent properties were investigated by fluorescence spectrophotometry. The excitation spectra of all composites indicated that the TCA matrix probably affected the energy absorption and transfer of organic ligands. In TCA/Eu0.5Tb0.5(AA)3Phen composites the introduced Tb3+ ions had some influence on energy absorption and transfer of organic ligands; the energy transfer process of the complex is suggested to be as follows: Phen→AA→Tb3+ion→Eu3+ion. The emission spectra indicated that the luminescent intensity of the TCA/Eu0.5Tb0.5(AA)3Phen composites was noticeably stronger than that of the TCA/Eu(AA)3Phen composites, suggesting that the comparatively stable and high-efficiency energy transfer process was only slightly influenced by the TCA matrix. In summary, the TCA/Eu0.5Tb0.5(AA)3Phen (90/10) composite possesses fine luminescent properties for potential usage as red fluorescent materials.  相似文献   

17.
The monitoring of variations in the luminescence intensity (I lum) of nanostructures of Eu(MBTA)3phen (MBTA is p-methoxybenzoyl trifluoroacetonate) complexes formed in aqueous solutions upon the introduction of anions is proposed as a method of analyzing the composition of Eu(III), Gd(III) and Lu(III) phosphate complexes in solutions with [PO 4 3? ] < [Ln]. It is found that low-lability binuclear complexes, which rearrange within an hour or longer, are formed in these solutions. It is shown that the lability of Ln(III) carbonate complexes exceeds the lability of Ln(III) complexes with PO 4 3? . An analysis of the dependence of I lum of the solution on the concentration of Eu(III) ions and on the time from the instant of the solution preparation shows that, in aqueous solutions where the concentration of anions is higher than the concentration of Ln(III) ions, nanostructures of Eu(III) phosphate and carbonate salts are formed in the range of Ln(III) concentrations 0.5–5 μM at concentrations of anions on the order of 10 μM and at concentrations of exceeding 100 μM. The rearrangement of these nanostructures to nanostructures of Eu(MBTA)3phen complexes is studied.  相似文献   

18.
A ligand with double sulfinyl groups, naphthyl-naphthalinesulphonylpropyl sulfoxide(dinaphthyl disulfoxide, L), was synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DTA, 1HNMR and UV spectra. The composition of these complexes, were RE2(ClO4)6·(L)5·nH2O (RE = La, Nd, Eu, Tb, Yb, n = 2 ∼ 6, L = C10H7SOC3H6SOC10H7). The fluorescent spectra illustrated that the Eu (III) complex had an excellent luminescence. It was supposed that the ligand was benefited for transferring the energy from ligand to the excitation state energy level (5D0) of Eu (III). The Tb (III) complex displayed weak luminescence, which attributed to low energy transferring efficiency between the average triplet state energy level of ligand and the excited state (5D4) of Tb (III). So the Eu (III) complex displayed a good antenna effect for luminescence. The phosphorescence spectra and the relationship between fluorescence lifetime and fluorescence intensity were also discussed.  相似文献   

19.
Complexes Eu(TTA)3phen and Eu(MBTA)3phen, as well as complexes Tb(MBTA)3phen and Tb(TTA)3phen, which do not luminesce in solutions, are shown to luminesce in polymer films (TTA is thenoyltrifluoroacetone, MBTA is n-methoxybenzoyltrifluoroacetone, and phen is o-phenanthroline). Luminescence of complexes of Eu and Tb in films of a polymer, poly(methylene-bis-anthranilamide) 1,6-hexamethylenedicarboxylic acid (PAA-5), having a high concentration of functional anthranilate groups, is studied. From the behavior of the luminescence intensity (I lum), the luminescence decay time, and the luminescence spectra of complexes of these lanthanides in polymer films, the following regular features were revealed. (i) During the film preparation at 90°C, Ln complexes are attached to PAA-5 via anthranilate groups. (ii) Irradiation of these films in the range of the absorption band of ligands (TTA or MBTA) leads to deactivation of the electronic excitation of ions according to the diketone detachment mechanism and to further binding of complexes to polymers. In this case, I lum(Eu(III)) decreases because the introduction of anthranilate groups of the polymer into the first coordination sphere of Eu(III) complexes enhances the nonradiative deactivation of these ions, whereas I lum(Tb(III)) increases since the introduction of these groups suppresses the nonradiative deactivation of Tb complexes through triplet states of ligands (TTA and MBTA). (iii) Upon storage of films in the dark (20°C), complexes detach themselves from the polymer and return to their initial structure. In PAA-5 films into which Eu and Tb complexes were simultaneously introduced, the color of the emission from the irradiation spot changes from red to green.  相似文献   

20.
Novel Schiff base ligands derived from N′-benzylidene-benzohydrazide (substituted by –H, ?CH3, ?OCH3, ?Cl) and 2-chloro-N-phenylacetamide were synthesized. The solid complexes of rare earth (Eu, Tb) nitrate with these Schiff base ligands were synthesized and characterized by elemental analysis, EDTA titrimetric analysis, thermal analysis, infrared spectra and UV–Vis spectra analysis. The fluorescence properties of rare earth (Eu, Tb) complexes in solid were studied. Under the excitation of ultraviolet light, these complexes exhibited characteristic emission of europium and terbium ions. The results showed that the ligand favored energy transfer to the emitting energy of Eu and Tb ions. Effects of different ligands on the fluorescence intensity of rare earth (Eu, Tb) complexes had been discussed. The electrochemical properties of rare earth (Eu, Tb) complexes were also investigated.  相似文献   

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