The synthesis, luminescence and energy transfer of the binary and ternary complexes of rare earth with aminobenzoic acids and 1,10-phenanthroline

Thirteen kinds of binary and ternary complexes of rare earth (Gd, Eu,Tb) with ortho (para) aminobenzoic acid and 1.10--phenanthroline were synthesized and characterized. The phosphorescence spectra and lifetimes of gadolinium complexes were measured and the lowest triplet state energies of ligands and the energy transfer efficiencies between ligands were determined. The luminescence properties and intramolecular energy transfer of these complexes were studied in details.

Luminescent properties of Ba-3(PO4)(2):Eu, Tb phosphors

Luminescence of europium (III), europium(II) and terbium(III) has been observed in Ba-3(PO4)(2):Eu, Tb phosphors which are synthesized in air atmosphere. The valence state of europium is influenced by amount of terbium. It is notable that the relative intensity of the emission spectra peaks corresponding to Eu2+ is increased if the amount of Tb3+ is increased. These phenomena can be explained by an electron transfer mechanism. We predict a new kind of two-rare-earth codoped trichromatic phosphors in Ba-3(PO4)(2) matrix.

The spectral properties of BaB8O13:Eu,Tb phosphors

The luminescence properties of BaB8O13:xEu,yTb phosphors which were synthesized in air atmosphere have been studied. The emissions of europium(III), terbium(III) and europium(II) have been observed in BaB8O13:xEu, yTb phosphors. Electron paramagnetic resonance (EPR) studies were carried out. The intensities of EPR peaks of europium(II) are increased if terbium(III) is increased in BaB8O13:Eu3+,yTb(3+) phosphors. So the valence state of europium is influenced by terbium(III). These phenomena can be explained by an electron transfer mechanism. We found a new kind of method to prepare trichromatic phosphor that two rare earth ions activated in a BaB8O13 matrix.

Electron transfer between Eu and Tb in MMgF(4) systems

Emission of europium(II) and europium(III) have been observed in SrMgF4 : xEu, yTb phosphors which are synthesized in Ar or Ar/H-2 flow. The valence state of Eu is influenced by terbium. It is notable that the intensities of the ESR peaks corresponding to EU(2+) are regularly changed when terbium ion is incorporated. The typical Tb3d XPS spectrum belonging to Tb4+ is also found when Eu is codoped. This phenomena can be explained by electron transfer mechanism Eu3+ + Tb3+-->EU(2+) + Tb4+. And its equilibrium constant is studied by ESR technique.

Luminescence properties of SrB4O7: Eu, Tb phosphors

In this paper, the luminescence properties of SrB4O7: xEu, yTb phosphors were investigated. The SrB4O7: xEu, yTb phosphors were first synthesized in air atmosphere, and the emission spectra of Eu2+, Eu3+ and Tb3+ ions have been observed in phosphors. We found that the relative intensity of the emission of Eu2+ ion in the same matrix are increased when Tb3+ is incorporated in SrB4O7:Eu phosphor. So the valence state of europium is influenced by terbium. These phenomena can be explained using an electron transfer theory.

Electron transfer between Eu3+ and Tb3+ in BaB4O7 matrix

The BaB4O7:Eu, Tb phosphors are first synthesized in air atmosphere. We investigate their luminescent properties, and find that europium(II) and europium(III) can coexist in the BaB4O7:Eu phosphor. We observed that the relative intensity of europium(II) is increased when terbium(III) is incorporated. The electron spin resonance (ESR) spectra are carried out. The intensity of ESR peaks corresponding to europium(II) is also increased when terbium(III) is increased, so the valency state of europium is influenced by terbium(III). We explain these phenomena by an electron transfer mechanism. (C) 1996 Academic Press, Inc.

The phase transitions of hetero atoms substituted molecular sieves Me-VPI-5(Me=Mg, Ti, Sn, Si) and their influence on spectra structures of Eu(III) ion

The hetero atom substituted aluminophosphate molecular sieves Me-VPI-5(Me = Mgt Ti, Sn, Si) were synthesized hydrothermally. Rare earth ions are originally doped into these microporous materials by aqueous solution ion exchange procedures. The phase transitions of the microporous materials are investigated by high-temperature and high-pressure experimental techniques. The influence of the phase transitions on the rare earth ions' spectral structures is discussed, With the increase of temperature, Eu(II)Mg-VPI-5 is converted into Eu(II)Mg-AIPO(4)-8, then into tridymite phase. The pressure has a notable influence on Eu(II) ion's spectral structures. The spectral structures have changed regularly with the increase of pressure.

ELECTRON-TRANSFER BETWEEN EU AND TB IN COMPLEX FLUORIDES

Europium (II) and europium (III) have been observed in MMgF(4):xEu, yTb (M=Ca, Sr, Ba) phosphors using their typical photoluminescence spectra when are synthesized in Ar or an Ar/H-2 stream. The valence state of Eu is influenced by terbium. It is notable that the intensities of the electron spin resonance peaks corresponding to Eu2+ change in a regular way when terbium ions are incorporated which can be explained by an electron transfer mechanism.

OBSERVATION OF EU2+ AND TB4+ IN SRMG4-EU8+, TB8+

Europium(II) and terbium(LV) drive boon observed in SrMgF4: Eu3+, Tb5+ phosphors which are synthesized in Ar stream. The valence state of europium is influenced by terbium. It is notable that the intensities of electron paramagnetic resonance (EPR) peaks corresponding to Eu2+ are increased when Tb3+ ion is incorporated in SrMgF4:Eu3+ phosphors, while X-ray photoelectron spectra of Tb-8d5/2 in SrMgF4:Eu3+,Tb3+ shows an additional peak at high energy to that of Tb-3d5/2 in SrMgF4: Tb3+, which is due to Tb4+. These phenomena can be explained by an electron transfer mechanism.

MOSSBAUER-EFFECT STUDIES OF A NEW ORGANOEUROPIUM COMPLEX [EU(ETA-6-C6ME6)(ALCL4)2]4

The Mossbauer spectrum of a new organoeuropium complex with a neutral pi-ligand, Eu(eta6-C6Me6) (AlCl4)2, is measured at 88 K. The Mossbauer parameters derived from the spectrum show the divalent nature of the europium ion in this organoeuropium complex. The calculations of the electric field gradient at the Eu nucleus in the crystal indicate that the Eu-Cl bond in the compound may possess a certain covalent character. The low Debye temperature of this complex may be attributed to weak and delocalized pi-bonding between the Eu atom and the benzene ring of hexamethylbenzene, and a slow paramagnetic relaxation is suggested by the Mossbauer effect.

Electron transfer between Eu3+ and Ce3+ in SrM-F-4 matrix

Emissions of europium (II) and europium (III) have been observed in SrMgF4:Eu and SrMgF4:Eu,Ce phosphors which are synthesized in Ar flow, It is notable that the intensity of the ESR peaks corresponding to Eu2+ is increased when cerium ion is incorporated which can be explained by electron transfer mechanism.

Electron Transfer and its Equilibrium between Eu and Tb in SrMgF4 System

Emission of europium(II) and europium(III) have been observed in SrMgF4 xEu, yTb phosphors winch are synthesized in Ar flow. The valence state of En is influenced by terbium, It is noted that the intensities of the ESR peaks corresponding to Eu2+ are increased when terbium ion is codopech this can be explained by electron transfer mechanism which is Eu3++Tb3+-->Eu2++Tb4+. And its equilibrium constant is calculated.

SYNTHESIS AND CHARACTERIZATION OF POLYMER-SUPPORTED LANTHANIDE COMPLEXES AND BUTADIENE POLYMERIZATION BASED ON THEM

Poly(styrene-acrylic acid)-lanthanide (Ln.PSAA) and poly(ethylene-acrylic acid)-neodymium (NdPEAA) complexes have been prepared and characterized. The infrared and X-ray photoelectron spectra indicate that the lanthanide complexes possess the bidentate carboxylate structure Ln-O-C(R)-O (see structure B in text). The catalytic behavior of the complexes has been described. The catalytic activities of Nd.PSAA and Nd.PEAA are much greater than that of the corresponding low molecular weight catalyst for butadiene polymerization. The activities of various individual lanthanide elements are quite different from one another. Neodymium shows the highest activity. Europium, samarium and the heavy elements exhibit very low or no activities. The cis-1,4 content of the polybutadiene obtained is not affected by different lanthanide elements in the series. The complex with the intermediate content of the functional group has a higher activity than the others. The polymer-supported lanthanide complexes having different constitutions have different catalytic activities. When the molar ratio of lanthanide to the functional group is ca. 0.2, the activity of the complex is in the optimum state. The activity is influenced by the dispersion of the lanthanide metal immobilized on the polymer chain. Catalytic activity can be improved by adding other metals to the catalyst system.

MOSSBAUER-EFFECT STUDIES OF THE DIMER OF A BIMETALLIC EU-AL COMPLEX

Mossbauer spectra of the dimer of a bimetallic Eu-Al complex, [(CF3COO)3EuHAl(C2H5)2 . 2 THF]2 are measured at different temperatures (81 to 166 K) and some Mossbauer parameters, such as isomer shift, electric quadrupole splitting and asymmetric parameter, are derived from the experimental spectra. The Debye temperature of the compound determined by a Debye model is 128 K. The results indicate that europium in the organo-europium compound is trivalent and that a bridging hydrogen atom between two europium atoms exists in the dimer. The low Debye temperature implies that the weaker binding force between the europium atom and the lattice may be related to the structure and the chemical bonding in the organometallic compound of europium.