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1.
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   

2.
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   

3.
Sol-gel glasses with covalently linked lanthanide complexes are luminescent materials which can be processed at ambient temperatures, which have a good solubility and uniform distribution of the complexes in the host matrix. In this study, a luminescent terbium(III) complex was covalently coupled to an organic-inorganic hybrid material prepared by the sol-gel process. This was realised by use of nicotinate groups as the ligands for the terbium(III) ion. The [Tb(C5H4NCO2)3(phen)(H2O)2] complex was immobilised on the sol-gel glass matrix and showed a green photoluminescence upon irradiation with ultraviolet light. The nicotinate groups act as an antenna to absorb the incident light and channel the excitation energy to the terbium(III) ion. The sol-gel glass was also prepared for the corresponding europium(III) complex. In this case, excitation of the europium(III) ion was possible via both the nicotinate ligands and the 1,10-phenanthroline ligands. High-resolution luminescence and excitation spectra were recorded and the radiative lifetimes were measured.  相似文献   

4.
A novel europium(III) complex, tris(dibenzoylmethanate){1-[9-hexyl-9H-carbazole]-2-(2-pyridyl)-benzimidazole}europium(III) [Eu(DBM)3(CAR-PyBM)] functionalized by a carbozole fragment, was synthesized and used as emitting material in organic electroluminescent (EL) devices. Compared with the device based on an unfunctional Eu(III) complex, [Eu(DBM)3HPyBM] (HPyBM=2-(2-pyridyl)benzimidazole), the EL performances of the device using [Eu(DBM)3(CAR-PyBM)] as an emitter was significantly enhanced due to the improvement of hole-transporting ability. The maximum efficiency and luminance of red emission achieved from the device with the configuration of ITO/N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′diamine (TPD, 50 nm)/ [Eu(DBM)3(CAR-PyBM)] (30 nm)/1,3,5-tirs-(N-phenylbenzimidazol-2-yl)benzene (TPBI, 20 nm)/LiF (1.5 nm)/Al were 4.2 cd/A and 200 cd/m2, respectively.  相似文献   

5.
Complexes of Eu(III) with mixed macrocyclic azacrown ethers and 1,10-phenanthroline (phen) were synthesized and their luminescence properties measured. The specific azacrown ethers used were 1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetraacetate (TETA) and 1,4,8,12-tetraazacyclopentadecane ([15]aneN4). The phen-coordinated complexes excited by UV light produced a very bright red emission via an intra-molecular energy transfer from phen to Eu(III). For [Eu(TETA)·(phen)·(H2O)] and [Eu([15]aneN4)·(phen)2]3+, the quantum yields of sensitized luminescence were 8.4% and 7.8%, respectively, and were much greater than those from non-sensitized luminescence of 1.2% and 4.4%, respectively. The decay times of the corresponding phen-coordinated complexes, as measured at room temperature, were 1.6 and 0.6 ms, respectively, and were much longer than those of the phen-uncoordinated complexes of 0.3 and 0.2 ms, respectively.  相似文献   

6.
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   

7.
Three kinds of europium complexes; Eu(phen)2Cl3(H2O)2, Eu(DN-bpy)phenCl3(H2O)2 and Eu(DB-bpy)phenCl3(H2O)2 (phen: 1,10-phenanthroline, DN-bpy: 4,4′-Dinonyl-2,2′-dipyridyl, DB-bpy: 4,4′-Di-tert-butyl-2,2′-dipyridyl) were prepared and then incorporated into polymethyl methacrylate (PMMA) matrix with different molar ratios of CO groups/Eu3+ ions. The final solid composites were formed by a self-assembly process among Eu3+ ion, the ligands and PMMA during the solvent evaporation process, and then the ligands re-coordinate to Eu(III). It was found that the ligands affect not only the emission properties of the pure complexes, but also the miscibility of the complexes and PMMA. More than one kind of symmetric sites of Eu3+ ions were formed in the composites due to the coordination of CO in PMMA to Eu3+ ions. The micro-environments of Eu(III) in the composites were changed with the compositions and the ligands, leading to the change in the crystalline structure, and consequently, the emission characteristics.  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.
A series of Ln(III) complexes with pyridine carboxylic acid-N-oxides (L) Ln-L, and mixed ligand complexes of Ln-L plus bipyridine (bipy) or 1,10-phenanthroline (O-phen) (X) Ln-L-X have been studied. These complexes were characterized in solution using Nd(III) absorption in the spectral range of the 4I9/24G5/2 transition corresponding to the hypersensitive band, and in the solid state with the use of IR and Eu(III) luminescence spectroscopy. In solutions a series of Nd(III) complexes and mixed ligand complexes has been examined and the formation of binary LnL and LnL2 complexes and mixed ligand LnL2X complexes evidenced. Solid complexes of Eu(III) with nicotinic acid N-oxide and ternary with nicotinic acid N-oxide plus phen were studied with the use of Eu(III) luminescence lifetime measurements and IR spectroscopy, proving the formation of binary [Eu(nicN-oxide)3(H2O)2].2H2O and ternary [Eu(nicN-oxide)3phen].H2O complexes.  相似文献   

10.
Tetranuclear europium(III) complexes, [Eu4(μ-O)(L1)10] (L1=2-hydroxy-4-octyloxybenzophenone,1) and [Eu4(μ-O)(L2)10] (L2=2-hydroxy-4-dodecyloxybenzophenone,2) were synthesized by the reaction of lanthanide nitrates with L1 or L2 in the presence of triethylamine in methanol. The photosensitized emission bands of the both Eu(III) complexes in THF-d8 were observed around 579, 590, 615, 653, and 699 nm by the excitation of the ligands at 380 nm, whereas the emission from the mononuclear complex 3 containing ethanol molecules was almost quenched. The emission efficiencies were determined to be 3.1±0.1% for 1 and 3.9±0.1% for 2, respectively. The differential scanning calorimetry (DSC) measurements demonstrated that the decomposition points of 1 and 2 were 309 °C and 320 °C, respectively, indicating high thermostability of these complexes compared to the mononuclear Eu(III) complex 3 (250 °C). New strategy for designing stable rare earth compounds giving strong emission would be emphasized by introducing polynuclear complexes. Polynuclear complexes should open a wide range of molecular design for photosensitized luminescence and thermal stability.  相似文献   

11.
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   

12.
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   

13.
In this paper, ligand effect of several bi-dental oxygen (O) and nitrogen (N) ligands on the red luminescence properties of europium ion (Eu3+) was studied comprehensively. Absorption, emission, and excitation spectral properties of ternary europium complexes with different combinations of ligands including thenoyl trifluoroacetone (TTA), naphthyl trifluoroacetone (NTA), 2,2′-bipyridyl (bpy) and phenanthroline (Phen) were investigated. Efficient Eu3+ red emission was observed with all the combinations of the above mentioned ligands. The most intense emission was found with the all nitrogen coordinated complex Eu(bpy)2(Phen)2 while the longest wavelength excitation band was recorded with oxygen-nitrogen mixed NTA-bpy complex Eu(NTA)1(bpy)3. With change of the ligands combination and ratio, the Eu3+ emission peak changes slightly from 612 to 618 nm. The absorption and excitation spectra of the europium complexes were compared and analyzed referring to the individual absorption spectral properties of the ligands. The relation between ligand-to-metal charge transfer states and luminescence intensities for different complexes was studied.  相似文献   

14.
Synthesis and photoluminescence behaviour of six novel europium complexes with novel β-hydroxyketone ligand, 2-(4-chlorophenyl)-1-(2-hydroxy-4-methoxyphenyl)ethan-1-one (CHME) and 2,2′-bipyridine (bipy) or neocuproine (neo) or 1,10-phenanthroline (phen) or 5,6-dimethyl-1,10-phenanthroline (dmphen) or bathophenanthroline (bathophen) were reported in solid state. The free ligand CHME and europium complexes, Eu(CHME)3.2H2O [1] Eu(CHME)3.bipy [2], Eu(CHME)3.neo [3], Eu(CHME)3.phen [4], Eu(CHME)3.dmphen [5] and Eu(CHME)3.bathophen [6]were characterized by elemental analysis, FT-IR and 1H-NMR. The photoluminescence emission spectra exhibited four characteristic peaks arising from the 5D0 → 7FJ (J = 1–4) transitions of the europium ion in the solid state on monitoring excitation at λex = 395 nm. The luminescence decay curves of these europium complexes possess single exponential behaviour indicating the presence of a single luminescent species and having only one site symmetry in the complexes. The luminescence quantum efficiency (η) and the experimental intensity parameters, Ω 2 and Ω 4 of europium complexes have also been calculated on the basis of emission spectra and luminescence decay curves. In addition, the antimicrobial and antioxidant activities were also studied of the investigated complexes.  相似文献   

15.
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   

16.
This work reports the energy transfer mechanism process of [Eu(TTA)2(NO3)(TPPO)2] (bis-TTA complex) and [Eu(TTA)3(TPPO)2] (tris-TTA complex) based on experimental and theoretical spectroscopic properties, where TTA=2-thienoyltrifluoroacetone and TPPO=triphenylphosphine oxide. These complexes were synthesized and characterized by elemental analyses, infrared spectroscopy and thermogravimetric analysis. The theoretical complexes geometry data by using Sparkle model for the calculation of lanthanide complexes (SMLC) is in agreement with the crystalline structure determined by single-crystal X-ray diffraction analysis. The emission spectra for [Gd(TTA)3(TPPO)2] and [Gd(TTA)2(NO3)(TPPO)2] complexes are associated to T→S0 transitions centered on coordinated TTA ligands. Experimental luminescent properties of the bis-TTA complex have been quantified through emission intensity parameters Ωλ (λ=2 and 4), spontaneous emission rates (Arad), luminescence lifetime (τ), emission quantum efficiency (η) and emission quantum yield (q), which were compared with those for tris-TTA complex. The experimental data showed that the intensity parameter value for bis-TTA complex is twice smaller than the one for tris-TTA complex, indicating the less polarizable chemical environment in the system containing nitrate ion. A good agreement between the theoretical and experimental quantum yields for both Eu(III) complexes was obtained. The triboluminescence (TL) of the [Eu(TTA)2(NO3)(TPPO)2] complexes are discussed in terms of ligand-to-metal energy transfer.  相似文献   

17.
A new europium complex [Eu(Pic)2(H2O)(EO4)](Pic)·0.75H2O was synthesized and used as the emission material for the single layer device structure of ITO/EO4–Eu–Pic/Al, using a spin-coating technique. Study on the optical properties of the [Eu(Pic)2(H2O)(EO4)](Pic)·0.75H2O complex where EO4=tetraethylene glycol and Pic=picrate anion, had to be undertaken before being applicable to the study of an organic light emitting diode (OLED). The electrical property of an OLED using current–voltage (IV) measurement was also studied. In complex, the Eu(III) ion was coordinated with the EO4 ligand as a pentadentate mode, one water molecule, and with two Pic anions as bidentate and monodentate modes, forming a nine-coordination number. The photoluminescence (PL) spectra of the crystalline complex in the solid state and its thin film showed a hypersensitive peak at 613.5–614.9 nm that assigned to the 5D07F2 transition. A narrow band emission from the thin film EO4–Eu–Pic was obtained. The typical semiconductor IV curve of device ITO/EO4–Eu–Pic/Al showed the threshold and turn on voltages at 1.08 and 4.6 V, respectively. The energy transfer process from the ligand to the Eu(III) ion was discussed by investigating the excitation and PL characteristics. Effect of the picrate anion on the device performance was also studied.  相似文献   

18.
New lanthanide complexes with benzeneseleninic (ABSe) and 4-chloro-benzeneseleninic (ABSeCl) acids have been synthesized and characterized by elemental analysis, infrared and UV–visible spectroscopies. The emission spectra of the trivalent europium complexes presented the typical electronic 5D07FJ transitions of the ion (J=0–4). The ground-state geometries of the europium complexes have been calculated by using the Sparkle/AM1 model. From these results, the 4f–4f intensity parameters and energies of the ligand singlet and triplet excited states have been obtained. The lower emission quantum yield for the [Eu(ABSe)3(H2O)2](H2O)2 compound, as compared to the [Eu(ABSeCl)3(H2O)2] one, can be associated to the higher numbers of water molecules, in the first and second coordination spheres, that contribute to the luminescence quenching. The [Eu(ABSe)3(H2O)2](H2O)2 complex presents an intermediate state whose energy difference with respect to the first excited singlet state is resonant with three phonons from the water molecules, favouring a multiphonon relaxation process from the singlet state followed by a fast internal conversion process; this effect is less pronounced in the complex with the ABSeCl ligand. The luminescence decay curves of the gadolinium complexes indicate that the level responsible for the intramolecular energy transfer process has a triplet character for both compounds. The nephelauxetic effect in these compounds was investigated under the light of a recently proposed covalency scale based on the concept of overlap polarizability of the chemical bond.  相似文献   

19.
Two novel, mixed ligand complexes of cobalt(III) and nickel(II), [Co(phen)2(taptp)]3+ (1) and [Ni(phen)2(taptp)]2+ (2) (phen = 1,10-phenanthroline and taptp = 4,5,9,18-tetraazaphenanthreno [9,10-b]triphenylene), were synthesized and characterized by elemental analyses, UV-visible and NMR spectroscopies. The binding interactions of the two complexes with DNA have been investigated using absorption and emission spectroscopy methods and electrophoresis measurement mode. The intrinsic binding constants for these complexes to DNA are in the order of 105. In Tris buffer, the Co(III) complex shows a moderate luminescence which was enhanced after binding to DNA. However for complex Ni(II), no emission was observed in Tris buffer. The [Co(phen)2(taptp)]3+ and [Ni(phen)2(taptp)]2+ can cause the photocleavage of DNA supercoiled pBR322 upon irradiation by 360 nm light. Based on the data, an intercalative mode of DNA binding is suggested for the two complexes.  相似文献   

20.
A β-diketone, 2-acetylfluorene-4,4,4-trifluorobutane-1,3-dione (HAFTFBD), and its three europium(III) complexes, Eu(AFTFBD)3⋅2H2O, Eu(AFTFBD)3(TPPO)2 and Eu(AFTFBD)3phen, were designed and synthesized, where TPPO was triphenylphosphine oxide and phen was 1,10-phenanthroline. The complexes were characterized by IR, UV-visible, photoluminescence (PL) spectroscopy and thermogravimetric analysis (TGA). The results show that the Eu(III) complexes exhibit a high thermal stability,and wide and strong excitation bands when monitored at 613 nm. Excited by ∼395 nm near UV light, the complexes emitted strong and characteristic red light due to ff transitions of the central Eu3+ ion, and no emission from the ligands was found. The photoluminescence mechanism of the europium(III) complexes was investigated and proposed as a ligand-sensitized luminescence process. Among the three europium(III) complexes, Eu(AFTFBD)3phen exhibits the highest thermal stability and the most excellent photoluminescence properties. A bright red light-emitting diode was fabricated by coating the Eu(AFTFBD)3phen complex onto an ∼395 nm-emitting InGaN chip, and the LED showed appropriate CIE chromaticity coordinates (x=0.66, y=0.33). A white LED with CIE chromaticity coordinates (x=0.32, y=0.32) was prepared with Eu(AFTFBD)3phen as red phosphor, indicating that Eu(AFTFBD)3phen can be applied as a red component for fabrication of near ultraviolet-based white light-emitting diodes.  相似文献   

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