A Mechanism of the influence of Gd(III) and other Ln(III) ions on sensitized luminescence of Eu(III) and Tb(III) ions in aqueous and ethanol solutions: The role of hydroxyl bridges

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 τ_lum 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 τ_lum 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).     

邻苯二甲酸铕—铽络合体系的荧光性能和红外光谱研究

本文对在３６５ｎｍ波长紫外光激发下均可发出特征荧光的铕、铽邻苯二甲酸固体络合物以机械混合和化学作用两种混合方式，研究了这两系列混合络合物的荧光光谱和红外光谱。结果表明，无论其荧光发射波长还是其发射强度，铕、铽之间均存在相互影响；其中荧光发射峰位的变化较小，而荧光强度变化较大，铕、铽的荧光性能之间即存在相互敏化作用，又存在相互猝灭作用。红外光谱结果表明机械混合和化学作用都使络合物的结构发生了变化。     

Surface dynamics and reconstruction of Si and Ge

The dynamical behavior of a Si(III) and a Ge(III) surface is studied. The formation of a superstructure, i.e. the surface reconstruction, is shown to be a consequence of the softening of surface phonons. Within our model we derive a (7×7) reconstruction for Si and an (8×8) reconstruction for Ge. A buckled model for the superstructure on Si(III) surface as well as on the Ge(III) surface is proposed.     

Influence of complexing ion on the fluorescence sensitization efficiency for oxazine dyes in nanoparticles of Sc,Eu, Sm,and Lu diketonates

The fluorescence sensitization regularities have been investigated for oxazine dyes (Nile blue, cresyl violet (oxazine-9), and oxazine-170) in nanoparticles of complexes of 2-naphthoyltrifluoroacetone with trivalent ions of rare-earth metals. The fluorescence sensitization efficiencies of dyes in nanoparticles from the Sc(III), Eu(III), Sm(III), and Lu(III) complexes are compared. It is shown that the fluorescence sensitization efficiencies of dyes in nanoparticles from the Sc(III), Eu(III), and Sm(III) complexes has similar values and greatly exceed that for nanoparticles from the Lu(III) complexes. The quantum yields of sensitized fluorescence are determined for dyes in nanoparticles from the Sc(III), Eu(III), and Sm(III) complexes. The nanoparticles doped with oxazine-170 from Eu(III) complexes are found to have the strongest fluorescence.     

Inert and stable erbium(III)-cored complexes based on metalloporphyrins bearing aryl-ether dendron for optical amplification: synthesis and emission enhancement

We have developed novel inert and stable erbium (Er)(III)-cored complexes based on metalloporphyrins for optical amplification. The functionalized metalloporphyrin ligands have been designed and synthesized to provide enough coordination sites for the formation of inert and stable 9-coordinated Er(III)-cored complexes. Er³⁺ ions were encapsulated by the metalloporphyrin ligands, such as Zn(II)- and Pt(II)-porphyrins. The near-infrared (IR) emission intensity of Er³⁺ ion is much stronger in the Er(III)-cored complex based on Pt(II)-porphyrin than Er(III)-cored complex based on Zn(II)-porphyrin. Furthermore, we have incorporated a G2-aryl-ether functionalized dendron into the Er(III)-cored complex, yielding an Er(III)-cored dendrimer complex bearing the Pt(II)-porphyrin. The Er(III)-cored dendrimer complex shows the stronger near-IR emission intensity than the corresponding complex based on Pt(II)-porphyrin by seven times in solid state. The lifetimes of the emission band of Pt(II)-porphyrin ligands in the visible region were found to be 30 and 40 μs for the Er(III)-cored complex and the Er(III)-cored dendrimer complex based on Pt(II)-porphyrin in deoxygenated THF solution samples, respectively. Also, in both cases, the sensitized luminescence intensity is increased in deoxygenated solution. Therefore, it indicates that the energy transfer from the metalloporphyrins to Er³⁺ ions takes places through the triplet state. In this paper, the synthesis and photophysical properties of novel Er(III)-cored complexes based on metalloporphyrins and Er(III)-cored dendrimer complex based on metalloporphyrin will be discussed.     

Synthesis and Luminescence Properties of Trivalent Rare-Earth Element-Doped Calcium Stannate Phosphors

The phosphors of calcium stannate activated with individual trivalent rare-earth element (REE) ions (Neodymium III, Europium III, Terbium III, Dysprosium III, and Samarium III) were synthesized by high-temperature solid-state reaction (SSR), and their characterization and luminescent properties were investigated. The crystal structures and morphologies of the resultant materials were well characterized by experimental techniques such as X-ray powder diffraction (XRD) and environmental scanning electron microscopy (ESEM). The XRD results display that the rare-earths substitution of Calcium II does not change the structure of calcium stannate host. Obviously, the ESEM image exhibits that phosphors aggregate and their particles with irregular shape exist. The calcined powders of the Europium III, Neodymium III, Samarium III, Dysprosium III, and Terbium III ions doped in calcium stannate exhibits bright red, reddish orange, yellowish, orange white, and green light, respectively. Although there is some intrinsic emission ranging from UV to near-infrared (NIR) due to the host lattice, the dominant signals are from the rare-earth sites, with signals characteristic of the trivalent rare-earth states. The emission spectrum from undoped-calcium stannate phosphor is characterized by two broad bands centered at ～800 and ～950 nm. The shapes of the emission bands are different for each dopant. The sharp emission properties show that the calcium stannate is a suitable host for rare-earth ion-doped phosphor material. Furthermore the influence of different rare-earth dopants, that is, Europium III, Neodymium III, Samarium III, Dysprosium III, and Terbium III, on thermally stimulated luminescence (TSL) of calcium stannate phosphor under the beta irradiation was discussed. Among these trivalent rare-earth-doped phosphors samarium-doped material showed maximum TSL sensitivity with favorable glow curve shape.     

Raman,FT‐IR,and DFT studies of 3,5‐pyrazoledicarboxylic acid and its Ce(III) and Nd(III) complexes

3,5‐Pyrazoledicarboxylic acid was used as a ligand for the synthesis of its Ce(III) and Nd(III) complexes. The complexes of Ce(III) and Nd(III) with 3,5‐pyrazoledicarboxylic acid were synthesized and their compositions were determined by elemental analysis. Vibrational study in the solid state of 3,5‐pyrazoledicarboxylic acid and its new Ce(III) and Nd(III) complexes was performed by IR and Raman spectroscopy. The changes observed between the IR and Raman spectra of the ligand and of the complexes allowed us to establish the coordination mode of the metal in both complexes. The comparative vibrational analysis of the free ligand and its lanthanide(III) complexes gave evidence that 3,5‐pyrazoledicarboxylic acid binds Ln(III) through the deprotonated carboxylic oxygens. The density functional theory (DFT) calculated geometries, harmonic vibrational modes and Raman scattering activities of the ligand were in good agreement with the experimental data, and a complete vibrational assignment is being proposed. The experimental IR and Raman bands of the ligand were assigned to normal modes on the basis of DFT calculations. The effect of the intramolecular hydrogen bonds in the ligand on vibrational mode positions is also discussed. The characteristic IR and Raman bands of 3,5‐pyrazoledicarboxylic acid and its lanthanide complexes were specified and discussed. Copyright © 2006 John Wiley & Sons, Ltd.     

Effect of the medium and the formation of nanostructures on deexcitation of electronic excitation of Eu(III) and Tb(III) chelates

The intensity I _lum and lifetime τ_lum 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 τ_lum 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 τ_lum 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 τ_lum of Eu(III) or Tb(III) caused by their incorporation into nanostructures.     

Synthesis and Fluorescence Properties of Lanthanide (III) Perchlorate Complexes with Bis(benzoylmethyl) Sulfoxide

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.     

Energy transfer study of the formation, composition, and size of nanostructures of metal ion complexes in aqueous solutions

We studied the luminescence intensity (I _lum) of the ions Eu(III) and Sm(III) in relation to the concentrations of ions Ln(III) and Al(III) in water at pH 7 at an excess of such beta-diketones as p-methoxybenzoyltrifluoroacetone (MBTA), dibenzoylmethane (DBM), and tenoyltrifluoroacetone (TTA) and in the presence of 1,10-phenanthroline (phen) used as a synergistic agent. Both the enhancement of I _lum (Eu(III)) upon addition of Gd(III) (co-luminescence) and the effect of the third ion are found to depend on the order of addition of the ions to the solution and, therefore, on the sequence of formation of nanostructures of complexes of these ions in the solution, in which the transfer of the triplet energy of the organic part of complexes takes place, leading to an enhancement in I _lum (Eu(III)). The intensity I _lum (Eu(III)) is shown to increase equally rapidly upon addition of either Gd(III) or Al(III) to solutions with DBM + phen. In solutions of all the three beta-diketones studied, the Eu(III) ions incorporate better into nanostructures of triply charged ions whose radius is similar to or smaller than the radius of the Eu(III) ions. Our study of the effect that the replacement of H₂O with D₂O exerts of I _lum of 5 × 10^?8 M Eu(III) at different concentrations of ligands shows that, at [Ln(III)] < [OH^?] and at a concentration of beta-diketones smaller than 3 × 10^?5 M, the deuteration affects I _lum(Eu(III)) and, therefore, the first coordination sphere of Eu(III) contains OH groups. It is shown that, in aqueous solutions with 3 × 10^?5 M TTA + 10^?5 M phen, the increase in I _lum(Eu(III)) caused by the introduction of Gd(III) ions results from two processes occurring in the nanostructures of these complexes: the energy transfer from Gd(III) complexes to Eu(III) complexes and the increase of I _lum of Eu(III) itself under the conditions in the solution where the total concentration [Ln] ? [OH^?] and both the photochemical deactivation of Eu(III) and the exchange of its excitation energy for vibrations of the OH groups are suppressed. The reliability of the size estimation of nanostructures of metal complexes is discussed in terms of the effect of these nanostructures on I _lum of chelates of Eu(III).     

Dual and multiple fluorescence mechanisms of p-dimethylaminobenzaldehyde and its trimethylene-bridged double molecule

p-Dimethylaminobenzaldehyde (DMABA, I) and its N-to-N trimethylene-bridged double molecule (III) exhibit dual or multiple fluorescences. Several mechanisms were proved to be responsible for the long-wave fluorescence bands: intramolecular solvent-assisted relaxation in the excited state (I and III); ground state aggregation at low temperatures (I in nonpolar solvents); excimer formation (III; and I only at high concentrations in some solvents). Intramolecular interaction in the ground state of III prepares an excimer-like structure. The dimer of DMBA aside of its own emission, may relax and emit an excimer-like fluorescence.     

Theoretical oscillator strengths for some transitions in P(III), As(III), Sb(III) and Bi(III)

Relativistic as well as non-relativistic oscillator strengths have been calculated for transitions in the principal sharp and diffuse series of P(III), As(III), Sb(III) and Bi(III) spectra. The radial integrals were computed by employing the wave functions obtained from a semiempirical method which included exchange effects. A comparison is presented for our calculated f_ik values with experimental and other theoretical data. The influence of relativistic effects on oscillator strengths for transitions in the P(III) through Bi(III) homologous sequence is discussed.     

Mössbauer spectroscopic characterization of iron methyl pyropheophorbide a and its derivatives

Two kinds of iron chlorophylls, i.e. (methyl pyropheophorbide a)iron(III) chloride and its bis-pyridine adduct, were prepared and characterized by⁵⁷Fe Mössbauer spectroscopy. (Methyl pyropheophorbide a)iron(III) chloride gave an asymmetric quadrupole-split doublet typical of high-spin iron(III) chlorophylls, while its bis-pyridine adduct showed a symmetric quadrupole-split doublet characteristic of low-spin iron(II) chlorophylls. The isomer shift and quadrupole splitting obtained for (methyl pyropheophorbide a)iron(III) chloride and its bis-pyridine adduct have led to the following conclusions. The substitution of the bulky phytyl group for the methyl group hardly affects the electronic state of the iron(II,III) ion, but the elimination of the methoxycarbonyl group increases the planarity of the macrocyclic chlorin ligand.     

叶绿素a锰（Ⅲ）和叶绿素a锰（Ⅱ）的合成和光谱

叶绿素ａ锰（Ⅲ）（Ｍｎ（Ⅲ）－Ｃｈｌ－ａ）由脱镁叶绿素（Ｐｈｅｏ－ａ）和醋酸锰（Ⅱ）合成而得，用反相高效液相色谱法分离纯化，叶绿素ａ锰（Ⅱ）（Ｍｎ（Ⅱ）－Ｃｈｌ－ａ）用Ｎａ２Ｓ２Ｏ４还原时绿素ａ锰（Ⅲ）获得，研究了它们的元素分析（ＥＡ），紫外可见吸附光谱（ＵＶ－Ｖｉｓ）和傅里叶红外吸收光谱（ＦＴ－ＩＲ）证明了此二种配合物的合成，并给出了（Ｍｎ（Ⅲ）－Ｃｈｌ－ａ）与（Ｍｎ（Ⅱ）－Ｃｈｌ－ａ）的组成分     

Theoretical Calculations of Transition Probabilities and Oscillator Strengths for Sc(III) and Y(III)

利用最弱受约束电子势模型理论计算了二价钪离子和二价钇离子的能级间跃迁几率和振子强度的数值. 二价钪离子的计算结果与美国国家标准技术研究院(NIST)所给出的可接受值吻合良好. 二价钇离子的计算结果也与现有的其他理论方法的计算结果十分接近.     

Fluorescence resonance energy transfer between cerium ion(III) and levofloxacin in micellar solution and its analytical application to the determination of levofloxacin

Fluorescence resonance energy transfer between cerium ion(III) and levofloxacin is studied in a micellar solution of cetyltrimethyl ammonium bromide. A non-fluorescent 1:2 complex was formed between excited cerium ion(III) and ground state levofloxacin. The fluorescence of cerium ion(III) is quenched by levofloxacin with the quenching in accordance with the Stern–Volmer relation. The analytical relationship was established between the ratio of the fluorescence of levofloxacin present and absent cerium ion (III) and the concentration of levofloxacin, which helped to estimate the content of levofloxacin directly.     

EPR and optical absorption characteristics of sodic plagioclase from granite pegmatite in Kadavur,India

The electron paramagnetic resonance (EPR) spectra of sodic plagioclase from dykes of granitic pegmatite occurring in the Kadavur area, Tamil Nadu, India, were examined at room temperature to identify paramagnetic impurities in a “low plagioclase” using EPR and optical techniques. The EPR spectra showed the presence of Fe(III) and Mn(II) impurities. After heating the plagioclase samples for various durations at 600 °C, it has been observed that the concentration of Mn(II) remained as such in one sample but completely disappeared in another sample, while there was no change in Fe(III) ion concentration after the heat treatment in either sample. Optical absorption spectra also showed Fe(II) and Fe(III) in addition to Ti(III) impurities in sodic plagioclase before heating, while after heating the relative concentration of Fe(II) and Fe(III) changed, accompanied by the disappearance of Ti(III).     

Preparation of polymer–rare earth complex using salicylic acid-containing polystyrene and its fluorescence emission property

Salicylic acid (SA) was first bonded onto the side chains of polystyrene (PS), obtaining functional macromolecule SAPS. Using the salicylic acid-containing polystyrene as a macromolecular ligand, a polymer–rare earth complex, SAPS–Eu(III), was prepared. The structure of SAPS–Eu(III) was characterized, and the fluorescence properties of SAPS–Eu(III) were mainly investigated. The experimental results show that the complex SAPS–Eu(III) has fine chemical stability because of the bidentate chelating effect of salicylic acid ligand. More important, the ligand SA on the side chains of PS can strongly sensitize the fluorescence emission of the center ion, Eu³⁺ ion, and it enables the complex SAPS–Eu(III) to produce the apparent “Antenna Effect”. In the diluted solution of the functional macromolecule SAPS, the formed complex SAPS–Eu(III) belongs to an intramolecular complex, or an intrachain complex. For the binary intramolecular complex SAPS–Eu(III), the apparent saturated coordination number of SA of SAPS towards Eu³⁺ ion is equal to 10, and here the binary intrachain complex SAPS–Eu(III) has the strongest fluorescence emission. On this basis, small-molecule 1,10-phenanthroline (Phen) acting as a co-ligand is added and the ternary complex SAPS–Eu(III)–Phen will be formed. As long as a small amount of Phen is added (in the molar ratio 1:1 (n(Phen):n(Eu))), the coordination of the two kinds of ligands, SA of SAPS and Phen, to Eu³⁺ ion will reach complete saturation, and here the fluorescence emission of the ternary complex will be further enhanced via the complementary coordination effect in comparison with that of the binary complex SAPS–Eu(III).     

Bond lengths and valences in BaBiO3

Bond length-bond strength correlations are developed for Bi(III) and Bi(V) oxides. Application to the two Bi sites in BaBiO₃ show that these are best described as Bi(III) and Bi(V) respectively, although there is a significant deviation from the ideal valence for the atom identified as Bi(III).     

Synthesis,characterization and mesomorphic behaviour of lanthanide (III) 4-alkoxybenzoates

The lanthanide (III) 4-alkoxybenzoates [Ln(C_nH_2n?+?1OC₆H₄CO₂)₃, Ln?=?La (III), Pr (III), Nd (III), Eu (III), Gd (III), Tb (III) and Dy (III) and n?=?6, 8, 10, 12 and 16] have been synthesized and characterized by elemental analyses, magnetic susceptibility measurements, and IR and electronic spectroscopy. Hot-stage polarizing optical microscopy and differential scanning calorimetry have been used to investigate the mesomorphic behaviour. The chain length influences the structure and hence the thermal behaviour of these compounds. All the lanthanide complexes except decyloxy derivatives exhibit smectic A mesophase. The decyloxy-containing complexes are non-mesomorphic. The differential scanning calorimeter traces do not display the exothermic peak for all the compounds except for the hexadecyloxy derivatives, which exhibit enantiotropic smectic A phase. The influence of the lanthanide ions on the phase transition has also been clearly demonstrated.