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1.
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   

2.
A novel ligand with double sulfinyl groups, bis(benzylsulfinyl)methane, was synthesized by a new method and its two lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, 1HNMR and UV spectra. The results indicated that the composition of these complexes was REL2.5(ClO4)3·3H2O (RE = Tb (III), Dy (III), L = C6H5CH2SOCH2SOCH2C6H5). The FT-IR results revealed that the perchlorate group was bonded with the lanthanide ion by the oxygen atoms, and the coordination was bidentate. The fluorescent spectra illustrated that both the Tb (III) and Dy (III) complexes displayed characteristic fluorescence in solid state, especially for the Tb (III) complex, the peak of 5D4 → 7 F5 of the Tb (III) ion in 544 nm was stronger than that of others. It indicated that the Tb (III) complex could emit purer green fluorescence. By analysis fluorescence and phosphorescence spectra, it was found that the ligand had the advantage to absorb energy and transfer it to the Tb (III) and Dy (III) ions. The phosphorescence spectra and fluorescence lifetimes of the complexes were also measured.  相似文献   

3.
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   

4.
Two novel ternary rare earth complexes of Tb(III) and Dy(III) perchlorates with bis(benzoylmethyl) sulfoxide (L) and benzoic acid (L′) had been synthesized and characterized by elemental analysis, coordination titration analysis, molar conductivity, IR, TG-DSC, 1HNMR and UV spectra. The results indicated that the composition of these complexes was REL5L′(ClO4)2·nH2O (RE= Tb(III), Dy(III); L=C6H5COCH2SOCH2COC6H5, L′=C6H5COO; n = 6,8). The fluorescence spectra illustrated that the ternary rare earth complexes presented stronger fluorescence intensities, longer lifetimes and higher fluorescence quantum efficiencies than the binary rare earth complexes REL5·(ClO4)3·2H2O. After the introduction of the second ligand benzoic acid group, the relative fluorescence emission intensities and fluorescence lifetimes of the ternary complexes REL5L′(ClO4)2·nH2O (RE= Tb(III), Dy(III)) enhanced more obviously than the binary complexes. This indicated that the presence of both organic ligands bis(benzoylmethyl) sulfoxide and the second ligand benzoic acid could sensitize fluorescence intensities of rare earth ions, and the introduction of benzoic acid group was resulted in the enhancement of the fluorescence properties of the ternary rare earth complexes. The phosphorescence spectra were also discussed.  相似文献   

5.
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   

6.
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   

7.
Two novel ternary rare earth perchlorate complexes had been synthesized by using bis(benzoylmethyl) sulfoxide as first ligand (L=C6H5COCH2SOCH2COC6H5), salicylic acid as second ligand (L=C6H4OHCOO). The compounds were characterized by elemental analysis, TG-DSC and molar conductivities in DMF solution. The composition was suggested as [REL5L′](ClO4)2·nH2O (RE=Tb, Dy; n=6, 8 ). Based on IR, 1HNMR and UV spectra, it showed that the first ligand, bis(benzoylmethyl) sulfoxide (L), bonded with Tb(III), Dy(III) ions by the oxygen atom of sulfinyl group. The second ligand, salicylic acid group (L′), not only bonded with RE(III) ions by one oxygen atom of carboxyl group but also bonded with RE(III) ions by oxygen atom of phenolic hydroxyl group. In bis(benzoylmethyl) sulfoxide system, fluorescent spectra of the complexes showed that the luminescence of Tb(III), Dy(III) ions was enhanced by the second ligand salicylic acid. The ternary complexes had stronger fluorescence than the binary ones where only bis(benzoylmethyl) sulfoxide acted as ligand. Phosphorescent spectra of the two ligands indicated that the coordination of salicylic acid resulted in the matching extent increasing between the triplet state of ligand and excited state of the rare earths. The relationship between fluorescence lifetime and fluorescence intensity was also discussed.  相似文献   

8.
Complexation and photophysical properties of complexes of lanthanide ions, Ln(III), with diethyl(phthalimidomethyl)phosphonate ligand, DPIP, were studied. Interactions between Ln(III) and DPIP were investigated using Nd(III) absorption and Eu(III) and Tb(III) luminescence (emission and excitation) spectra, recorded in acetonitrile solution containing different counter ions (NO3-, Cl- and ClO4-). Results of the absorption spectroscopy have shown that counter ions play a significant role in the complexation of Ln(III)/DPIP complexes. Studies of luminescence spectra of Eu(III) and Tb(III) ions proved that the formation of Ln(III)/DPIP complexes of stoichiometry Ln:L=1:3 is preferred in solution. Based on the results of elemental analysis, Nd(III) absorption spectra and IR and NMR data, it was shown that the DPIP ligand binds Ln(III) ions via oxygen from phosphoryl group, forming complexes of a general formula Ln(DPIP)3(NO3)3·H2O, in which the NO3- ions are coordinated with the metal ion as bidentate ligands. Luminescent properties and energy transfer, from the ligand to Ln(III) ions in the complexes formed, were studied based on the emission and excitation spectra of Eu(III) and Tb(III). Their luminescent lifetimes and emission quantum yields were also measured.  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.
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   

11.
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   

12.
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   

13.
Five new europium(III) complexes Eu(p-EFBA)3.(H2O)2 (C1), Eu(p-EFBA)3.neo (C2), Eu(p-EFBA)3.batho (C3), Eu(p-EFBA)3.phen (C4), Eu(p-EFBA)3.bipy (C5) have been synthesized by using ethyl-(4-fluorobenzoyl) acetate (p-EFBA) as β-ketoester ligand and neocuproine (neo), bathophenanthroline (batho), 1,10-phenanthroline (phen) and 2,2-bipyridyl (bipy) as ancillary ligands. The synthesized complexes C1-C5 were characterized by elemental analysis, nuclear magnetic resonance spectroscopy (1H-NMR), infrared (IR) spectroscopy, thermogravimetric analysis (TG/DTG), UV-visible and photoluminescence (PL) spectroscopy. The relative study of luminescence spectra of complexes with the previously reported complexes of isomeric ligand (ortho and meta substituted ligand) indicate the higher luminescence properties of complexes as an effect of fluorine position on β-ketoester ligand. The para substituted ligand shows a remarkable effect on quantum efficiencies and Judd-Ofelt intensity parameters (Ω2, Ω4) of the complexes. The higher value of intensity parameter Ω2 associated with hypersensitive 5D0 → 7F2 transition of europium(III) ion revealing highly polarizable ligand field. The purposed energy transfer mechanism of complexes indicates the efficient energy transfer in complexes.  相似文献   

14.
Eu(III)-9-acridinecarboxylate (9-ACA) complex was synthesized and characterized by elemental analysis, conductivity measurement, IR spectroscopy, thermal analysis, mass spectroscopy, 1H-NMR, fluorescence and ultraviolet spectra. The results indicated that the composition of this complex is [Eu(III)-(9-ACA)2(NCS)(C2H5OH)2] 2.5 H2O and the oxygen of the carbonyl group coordinated to Eu(III). The interaction between the complex with nucleotides guanosine 5′- monophosphate (5′-GMP), adenosine 5′-diphosphates (5′-ADP), inosine (5′-IMP) and CT-DNA was studied by fluorescence spectroscopy. The fluorescence intensity of Eu(III)-9-acridinecarboxylate complex was enhanced with the addition of CT-DNA. The effect of pH values on the fluorescence intensity of Eu(III) complex was investigated. Under experimental conditions, the linear range was 9–50 ng mL−1 for calf thymus DNA (CT- DNA) and the corresponding detection limit was 5 ng mL−1. The results showed that Eu(III)-(9-ACA)2 complex binds to CT-DNA with stability constant of 2.41 × 104 M .  相似文献   

15.
This work reports on the photoluminescent properties of three new lanthanide complexes with acetoacetanilide (aaa), a β-diketonate ligand. The complexes have the general molecular formulae [RE(aaa)3(H2O)], they are soluble in organic solvents such as ethanol and chloroform and insoluble in water. The energy of the triplet state was determined at about 4,700 cm?1 higher than the 5D4 emitting level of the Tb(III) ion, leading to an absolute quantum yield of 22 % for the [Tb(aaa)3(H2O)] complex. The photoluminescent properties were studied and the luminescence parameters of the [Eu(aaa)3(H2O)] complex were experimentally determined. The photostabilities of the complexes under continuous UV irradiation were measured and the data indicate low stability of the [Tb(aaa)3(H2O)] complex when the system is excited at the band attributed to energy transfer from the ligand to terbium(III) ion. However, its photostability is significantly improved under inert atmosphere.  相似文献   

16.
Two novel ternary rare-earth complexes SmL5·L·(ClO4)2·7H2O and EuL5·L·(ClO4)2·6H2O (the first ligand L = C6H5COCH2SOCH2COC6H5, the second ligand L = C6H4OHCOO) were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, 1HNMR and UV spectra. The detailed luminescence studies on the rare-earth complexes showed that the ternary rare-earth complexes presented stronger fluorescence intensities, longer lifetimes, and higher fluorescence quantum efficiencies than the binary rare-earth materials. After the introduction of the second ligand salicylic acid group, the relative emission intensities and fluorescence lifetimes of the ternary complexes LnL5·L·(ClO4)2·nH2O (Ln = Sm, Eu; n = 7, 6) enhanced more obviously than the binary complexes LnL5·(ClO4)3·2H2O. This indicated that the presence of both organic ligand bis(benzoylmethyl) sulfoxide and the second ligand salicylic acid could sensitize fluorescence intensities of rare-earth ions, and the introduction of salicylic acid group was a benefit for the fluorescence properties of the ternary rare-earth complexes. The fluorescence spectra, fluorescence lifetime and phosphorescence spectra were also discussed.  相似文献   

17.
The absorption and emission spectra of a liquid-crystalline melt prepared on the basis of a synthesized mesogenic europium (III) adduct are studied in the temperature range from 77 to 348 K. The main channels and rate constants of intramolecular energy transfer from ligands to Eu (III) ions are determined from the absorption and luminescence spectra and luminescence kinetics of the sample under study. It is shown that the liquid-crystalline melt of the europium (III) adduct has a high photostability and an intense luminescence in the temperature range from 77 to 300 K, which allows one to consider it as a promising material for optoelectronic devices. Above room temperature, the relaxation time of the 5 D 0 level of Eu (III) ions sharply shortens. An analysis of the kinetics of the luminescence corresponding to the 5 D 07 F 2 transition shows that the relaxation of the 5 D 0 level in the temperature range from 300 to 348 K occurs through a charge-transfer state.  相似文献   

18.
Solid complexes of terbium and europium nitrates with an amino-alkenone type ligand, 1-[2-(6-methylpyridin-2-ylamino)-5,6-dihydro-4H-pyran-3-yl]ethanone (L) have been prepared and characterized by elemental analysis, conductivity measurements, and IR spectra. The crystal and molecular structures of the complexes [TbL2(NO3)3(H2O)]·CHCl3 (1) and [EuL2(NO3)3(H2O)]·CH3CO2C2H5 (2) have been determined by single crystal X-ray diffraction. And the coordination spheres of the complexes are similar. At the same time, the luminescent properties of the Tb3+ complex in solid state and in solvents were investigated at room temperature. Under the excitation of UV light, Tb(III) complex exhibited characteristic emissions but not for the Eu(III) complex. The lowest triplet state energy level of the ligand in the complex matches better to the resonance level of Tb(III) than Eu(III) ion.  相似文献   

19.
To explore the relationship between the structure of the ligands and the luminescent properties of the lanthanide complexes, a series of lanthanide nitrate complexes with two novel structurally related multipodal ligands, 1,3-bis{[(2’-(2-picolylaminoformyl))phenoxyl]methyl}benzene (L I ) and 1,2-bis{[(2’-(2-picolylaminoformyl))phenoxyl]methyl}benzene (L II ), have been synthesized and characterized by elemental analysis, infrared spectra and molar conductivity measurements. At the same time, the luminescent properties of the Eu(III) and Tb(III) nitrate complexes in solid state and the Tb(III) nitrate complexes in solvents were investigated at room temperature. Under the excitation of UV light, these complexes exhibited characteristic emissions of central metal ions. The lowest triplet state energy levels T1 of these ligands both match better to the lowest resonance energy level of Tb(III) than to Eu(III) ion. The influence of the structure of the ligands on the luminescent intensity of the complexes was also discussed.  相似文献   

20.
We have studied the spectral luminescence properties of mixed-ligand complexes of Eu(III) ions with tetracyclines and hydrogen peroxide. We have established that incorporation of hydrogen peroxide into the inner sphere of these complexes leads to a significant increase (by a factor of 10–25) in the intensity of luminescence of the Eu(III) ions, redistribution of the intensities of the 5D07Fj transitions, in particular to an anomalous increase in the intensity of the band for the forbidden transition 5D07F0. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 310–314, May–June, 2007.  相似文献   

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