RARE EARTH CONTAINING POLYMER TERNARY COMPLEXES AND THEIR FLUORESCENT PROPERTIES

Rare earth containing fluorescence active polymer ternary complexes were synthesized and their absorption and emission properties were investigated.

Studies on synthesis and fluorescent property of rare earth complexes RE(ABMF)_2AA and copolymers RE(ABMF)_2AA-co-MMA

Four new complexes RE（ABMF）2AA（RE=Sm, Eu, Tb, Dy） were synthesized by the reaction of RECl3·6H2O with acrylic acid（HAA） and 1-（2-furyl）-3-phenyl-1,3-propanedione（ABMF）.The copolymerization of the rare earth complexes with methyl methacrylate was studied by using 2,2-azobis-isobutyronitrile as an initiator.The composition and structure of the four complexes were characterized by elemental analysis, UV-vis and FTIR.The glass transition temperature and molecular weight of the copolymers were determined.Photolu-minescent measurement showed that ligand ABMF could efficiently transfer the energy to Sm^3＋ and Eu^3＋ ions in the complexes and sensitize the luminescence of the rare earth ions, but could not sensitize Tb^3＋ and Dy^3＋ ions.As a result, both Sm^3＋ and Eu^3＋ complexes emitted the characteristic fluorescence of Sm^3＋ and Eu3＋ ions due to the f-f transitions.The four copolymers could emit strong fluorescence of the rare earth ions.

Interaction between Ternary Rare Earth Complexes of Cinnamic Acid and Phenanthroline with DNA by Spectroscopy

The interaction of ternary complexes [RE(phen)(cin)_3(H_2O)](RE= Nd (III),Ce(III),Eu(III))with calf thymus DNA was investigated by electronic absorption spectroscopy, ethidium bromide(EB)-DNA quenching fluorescent spectra and resonance light scattering. All experimental results indicate that the three complexes bind to DNA by the electrostatic mode and the intercalative mode. It is predicted that these complexes show high anticancer activity or other biologic activity.

Direct microwave leaching conditions of rare earth elements in fluorescent wastes

The luminescent phosphor powder in the fluorescent lamp constitutes 2%of the lamp’s weight.It can be mentioned that fluorescent wastes are a crucial raw material to produce rare earth oxides.In the present study,microwave leaching process was conducted to dissolve rare earth elements yttrium(Y),europium(Eu),and remaining rare earth elements(REEs)present in the phosphor powder of the fluorescent lamp.and the yields were compared.In the microwave leaching process,the effects of the temperature(80-160℃),acid type(hydrochloric acid(HCl),nitric acid(HNO_(3)),sulphuric acid(H_(2)SO_(4))),acid concentration(0.5-6 mol/L),solid to liquid ratio(0.1:10-0.5:10)and reaction time(5-90 min)parameters on leaching efficiencies of varying rare earth elements and calcium were investigated.The highest yield was obtained in the direct microwave leaching of fluorescent waste with the experimental conditions of 6 mol/L HCl,160℃,0.1:10 solid-to-liquid ratio(S:L),and 90 min.Activation energy calculations were made,and kinetic models of the reactions were obtained,and it is observed that Y and Eu dissolution is diffusion-controlled,on the other hand,lanthanum(La),cerium(Ce),and terbium(Tb)were examined to be chemical reaction controlled.Moreover,calcium(Ca)and gadolinium(Gd)seem coherent with the mixed model.Concurrently,mathematical models of all experimental studies are created with the response surface Box-Behnken method and the correlation coefficients of all the models are over 90%.

Syntheses, characteristics, and fluorescence properties of complexes of europium with benzoic acid and its derivatives

The binary complexes of europium with benzoic acid and its derivatives(phthalic acid, m-phthalic acid, o-aminobenzoic acid, salicylic acid, and sulfosalicylic acid) weresynthesized and their compositions were identified by elemental analyses. UV and IR of the complexeshave been investigated. The UV spectra indicated that the complexes' ultraviolet absorption weremainly the ligands' absorption. The IR spectra showed that the IR spectra of complexes are differentfrom those of free ligands. The fluorescence properties of them were investigated by usingluminescence spectroscopy, the results showed that only three complexes appear as betterluminescence, they were Eu-benzoic acid, Eu-m-phthalic acid and Eu-phthalic acid, while the othersexhibited the ligands' wideband emission.

Synthesis, Characterization and Fluorescence of Terbium(Ⅲ) Complexes with Phenylglyoxylic Acid and 2,2-Dipyridine, 1,10-Phenanthroline, Triphenyl Phosphine Oxide

Three new complexes TbL3dipy （H2O）2, TbL3phen （H2O） 2 and TbL2 （TPPO） 2NO3 were synthesized （L = phenylglyoxylate ion, dipy = 2, 2-dipyridine, phen = 1,10-phenanthmline, TPPO = Triphenyl phosphine oxide）. Elemental analysis, conductivity, IR spectra, and ^1HNMR spectra studies were performed. IR spectra indicate that the carboxylate ion of phenylglyoxylate is coordinated to the Tb（Ⅲ） ion as an unidentate ligand. In ^1HNMR, the signals of different hydrogens in phenylglyoxylate ion shift upfield. The excitation and emission spectra of the three solid complexes were recorded at morn temperature, in which the optimum excitation wavelengths are, 361.0, 359.0 and 367.0 nm for these three complexes, respectively. Four emission bands due to the ^5D4-^7Fj（j = 6, 5, 4, 3） transitions were observed for TbL3dipy（H2O）2（489.0, 545.0, 584.0, 620.0 nm） and TbL3phen（H2O）2（490.0, 544.0, 583.0, 620.0 nm）. Under the same conditions, only one emission band due to the ^5D4-^7F5 transition was observed for the complex TbL2（TPPO）2NO3. The emission intensity of TbL3dipy（H2O）2 is the strongest among the three complexes.

Syntheses, characterization, and luminescence of two lanthanide complexes [Ln_2(acetate)_6(H_2O)_4]·4H_2O (Ln=Tb(1), Sm(2))

Two dinuclear compounds [Ln2（acetate）6（H2O）4]-4H2O （Ln=Tb（1）, Sm（2）） were obtained by the hydrothermal reaction of Ln2O3 with malonic acid at 150 ℃. Both compounds were characterized by elemental analyses, infrared spectra, and single crystal X-ray diffraction. The results showed that complexes 1 and 2 were isomorphous and crystallize in triclinic space group P 1. The coordination geometry around Ln（Ⅲ） ions in the complexes 1 and 2 was a distorted tricapped trigonal prism with a nine coordination. In the crystal, the molecular organization was further stabilized by well-defined weak hydrogen bonding interactions between the neutral dinuclear molecular units that led to the formation of a three-dimensional network. The fluorescence properties of the two complexes 1 and 2 in organic solvents were also studied. The results show that the ligand acetate favored energy transfer to the emitting energy level of Tb（Ⅲ） in complex 1. Some factors that influence the fluorescent intensity were also discussed in the article.

Synthesis and properties of Tb^(3+) isomultiligand complexes

Four kinds of terbium containing monomers were synthesized by the reaction of Tb isoproxides with acrylic acid and β diketones. The composition and structure of these monomers were confirmed by FT IR, UV spectroscopy and elemental analysis. DTA and TG analyses reveal that the decomposition temperature of these monomers is in the range of 190～200 ℃. The fluorescence properties of these monomers were studied. Under the excitation of UV light, these monomers exhibit characteristic luminescence of terbium ion, the fluorescent intensity is affected by the polarity of solvent and triplet state of ligand. In solid state, the monochromatic index of luminescence is enhanced.

Synthesis of a Polyaminopolycarboxylic Acid and Fluorescence of Tb^(3+) Complexes in Aqueous Solution

A new polyaminopolycarboxylic acid, diethylenetriamine N′,N bi( p acetoamino salicylic acid) N′,N″,N triacetic acid(DTPA·2pAS), has been synthesized DTPA·2pAs can sensitize the luminescence of Tb 3+ and Dy 3+ in aqueous solution Fluorescent titration at pH 7 0 indicated a 1∶1 composition of Tb 3+ to DTPA·2pAS for the complexes The complexes exhibit intensely sensitized fluorescence in a range of pH 5 0～12 0 The fluorescence intensity of the complexes increased as the concentration was raised from 1×10 -7 to 1×10 -4 mol/L, and then decreased at 1×10 -3 mol/L due to concentration quenching A replacement of EDTA with DTPA·2pAs in Tb 3+ EDTA complex solution led to increasement in Tb 3+ sensitized luminescence intensity, suggesting formation of Tb 3+ DTPA·2pAS complexes and higher stability of these complexes than those of Tb 3+ EDTA, which has been confirmed by determination of stability constants with pH potentiometric titration The results show that DTPA·2pAS may be applied to fluorescent immunoassay as a “fluorescence enhancement solution”

Synthesis, Characterization and Fluorescence Studies on Complexes of Terbium with Phenylglyoxylic Acid, 2,2-Dipyridine, 1,10-Phenanthroline, Triphenyl Phosphine Oxide

Three new complexes TbL3dipy （H2O）2, TbL3phen （ H2O ）2 and TbL2 （ TPPO ）2NO3 have been synthesized （L = phenylglyoxylate ion, dipy = 2, 2- dipyfidine, phen = 1,10-phenanthroline, TPPO = Triphenyl phosphine oxide ）. Elemental analysis, conductivity, IR spectra and ^1HNMR spectra studies were performed on them. IR spectra indicate that carboxylate ions in the phenylglyoxylate are coordinated to Tb （Ⅲ） ions as unidentate ligands. In ^1HNMR, the signals of hydrogens in phenylglyoxylate shift upfield. The excitation and emission spectra of the three comolexes were recorded at room temoerature, the excitation spectra show that the optimum excitation wavelengths are 361.0, 359.0 and 367.0 nm, respectively. Four emission bands due to ^5D4-^7Fj （j = 6, 5, 4, 3 ） transitions were observed for TbLadipy （ H2O ）2 （489.0, 545. 0, 584.0,620.0 nm） and TbL3phen （H2O）2 （490. , 544.0, 583.0, 620.0 nm）. And under the same conditions, only one emission band due to ^5Da-^7F5 transition was observed for TbL2 （TPPO）ENO3. The emission intensity of TbLadipy （H2O）2 is the strongest among the three complexes.

Synthesis,luminescent properties,and theoretical study of novel Sm^(3+) and Dy^(3+) complexes containing β-diketone and 1,10-phenanthroline

Two new ternary complexes of 1-（2-thienyl）-3-（p-phenylethynylphenyl）-1,3-propanedione（HTPP） and 1,10-phenanthroline（phen） with Sm^3＋ and Dy^3＋ were synthesized.The composition of the ternary complexes was characterized as Sm（TPP）3phen and Dy（TPP）3phen,respectively,by infrared（IR） spectra,chemical analysis,elemental analysis,and thermodynamic analysis.At room temperature,under UV light excitation,the Sm^3＋ and Dy^3＋ complexes exhibit characteristic emissions of the central ions.It is found that the fluorescence intensity of Sm（TPP）3phen is stronger than that of Dy（TPP）3phen.In order to explain this phenomenon,an accurate quantum chemistry calculation was carried out,and the result is in good agreement with the experiment data.

Fluorescence properties and application of doping complexes Eu_(l-x)L_x(TTA)_3Phen as light conversion agents

Light conversion agents Eul-xLx（TTA）3Phen (L denotes (La3+, Gd3+, Y3+)) complexes were prepared, and the influence of doping ions on fluorescence properties was investigated by elementary analysis, FTIR and fluorescent spectra. The results show that FTIR spectra of Eul-xLx（TTA）3Phen complex system are identical with that of EuTTA3Phen, which indicates that the complexes (Eul-xLx（TTA）3Phen) are similar in structure to （Eu （TTA）3Phen.） For the above doping elements, co-fluorescence enhancement has the following order: Gd3+>Y3+>La3+, and the optimum mole fractions of doping elements are 0.4, 0.2 and 0.5 respectively for Gd3+, Y3+, La3+. Among all the complexes, Eu0.6Gd0.4（TTA）3Phen complex has the strongest fluorescent intensity. Applying Eu0.6Gd0.4（TTA）3Phen complex to plastic and printing inks, bright red fluorescence plastic and printing inks are obtained when the content of europium reaches 0.1%（mass fraction）.

Synthesis and Fluorescence Property of Eu^(3+), Tb^(3+) Perchlorate Complexes with Diphenyl Sulfoxide and 1,10-Phenanthroline

Two ternary complexes of RE(ClO_4)_3-DPSO-phen and two binary complexes of RE(ClO_4)_3-phen have been synthesized (RE=Eu, Tb; DPSO=diphenyl sulfoxide, phen=1,10-phenanthroline). Elemental analysis and TG-DTA studies suggest that the ternary complexes consist of RE(ClO_4)_3(DPSO)(phen)_3·nH_2O (n=1, 3) and binary complexes consist of RE(phen)_4(ClO_4)_3. IR spectra studies indicate that the DPSO ligand is bonded with RE(Ⅲ) through oxygen atom in sulfinyl group and phen ligand is bonded to RE(Ⅲ) through nitrogen atom. The molar conductivities measured in the acetonitrile solution indicate that two inorganic anions ClO_4^- are coordinated and binary complexes are nonelectrolyte. In the fluorescent spectra it was found that the fluorescence emission intensity of the ternary complexes more intensive than that of the binary complexes.

Fluorescence Properties of Eu^(3+)/Gd^(3+)/Citric Acid Mixed Complexes Doping in Silicon Rubber Matrix

Series of doped rare earth compiexes-EuxGd(1-x) (CA)3·nH2O (CA = citric acid) were synthesized. Some characterizations were taken for these complexes. The experimental results shows that the doped rare earth complexes have the best fluorescence property when the ratio of Eu and Gd is from 0.7 to 0.3. Silicon rubber-based composites were prepared by mechanical blending the EuxGd(1-x) (CA)3·nH2O and silicon rubber. Then, the fluorescent property of the composites was studied. It is found that the fluorescence intensity of the composites increase linearly with the contents of the rare earth complexes increasing.

Synthesis and Properties of Ternary Europium Complexes with Aromatic Carboxylic Acid and Nitrogen-Containing Heterocyclic Ligand

Seven ternary Eu （m） complexes were synthesized with aromatic carboxylic acid （benzoic acid, phenylacetic acid, phenylpropionic acid and cinnamic acid） as the first ligand and 1,10-phenanthro- line or 2,2＇-dipyridyl as the second ligand. The ternary Eu（ Ⅲ ） complexes were characterized by elemental analysis, IR and TG-DTG methods. In these complexes, the Eu （Ⅲ） ions are bonded to the oxygen atoms of carboxylate and the nitrogen atoms of neutral ligands. Four complexes whose second ligand is 1,10- phenanthrolin have fine thermal stability. Excitation and luminescence spectra of the tide complexes reveal that the fluorescence of the complexes in which 1,10- phenanthrolin as the second ligand are more intensive than those complexes in which 2, 2＇-dipyridyl as the second ligand. The order of the strongest emission peak of seven ternary complexes is： Eu（β-PPA）3phen 〉 Eu（BA）3phen 〉 Eu（PLA）3phen 〉 Eu（BA）3bipy 〉 Eu （ PEA）3bipy 〉 Eu （ CA ）3phen · H2O 〉 Eu （ CA ）3bipy （BA ： benzoic ; PEA ： phenylacetic ; β-PPA ：

Synthesis, crystal structure, and fluorescence of two dimeric europium(III) complexes with 2-(trifluoromethyl)benzoate

Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synthesized by solvent method and determined by X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group Pi. Both are binuclear molecules with an inversion center. In complex 1, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu^3＋ ion is eight-coordinated with six O atoms from five 2-TFMBA ligands and two N atoms from one 2,2′-bipy molecule. In complex 2, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu^3＋ ion is nine-coordinated with seven O atoms from five 2-TFMBA ligands and two N atoms from one 1,10-phen molecule. The two complexes both exhibited strong red fluorescence under ultraviolet light, and the ^5D0→^7Fj （j=0-4） transition emissions of Eu^3＋ ion were observed in their emission spectra.

Structure and Fluorescence Emission of Hetero-Nuclear Complexes of Europium-Lanthanum Nitrates with N,N′-Substituted Adipamide

A europium lanthanum hetero nuclear complex with new ligand N, N′ dimethyl N, N′ diphenyladipamide (MPAA) was prepared. The one dimensional chain structure of [La 0.5 Eu 0.5 (MPAA) 2(NO 3) 3] was determined crystallographicaly. The europium ion and lanthanum ion statistically lie at the position of the metal ion with M=1/2(La+Eu). Each Ln 3+ ion is nine coordinated including three bidentate nitrates, three carboxyl groups from three MPAA molecules, in which two MPAA are act as bridge ligand. The intensity of fluorescence of La 3+ Eu 3+ heteronuclear complex A was obviously higher than that of pure Eu 3+ complex B both in solution and in solid state.

Synthesis and Fluorescent Property of Europium Ternary Complex-MMA Copolymer

Under the mild condition a new ternary rare earth complex Eu （ DBM ）2MA · 2H2O [ DBM： C6H5COCHCOC6H5; MA： CH2C（CH3）COO^- ] was synthesized by the reaction of EuCl3 with dibenzoylmethane and methacrylate in alcohol. A new bonded copolymer Eu（DBM）2MA-MMA was prepared by copolymerization of the Eu（DBM）2MA·2H2O complex with methyl methacrylate（MMA） monomer using AIBN as an initiator. The composition, structure and fluorescence properties of the complex and copolymer were characterized by means of elemental analysis, complex titration, IR, UV-VIS and fluorescent spectra. The thermal stability, glass temperature and average molecular weight of the copolymer Eu（DBM）2MA-MMA were determined by TG-DTA, DSC and GPC, respectively. The research results show that both of the ternary rare earth complex and the copolymer can emit strong Eu（Ⅲ） fluorescence at 613 nm.

Preparation of Eu(TTA)_2phen(MA)/SiR Fluorescent Materials under High Mechanical Blending Temperature

Eu（TTA）2（phen）（MA） complexes were synthesized, in which MA was introduced as the acidic ligand to increase the fluorescent intensity of the complexes. The complexes were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, and fluorescent spectra, respectively. Different amounts of rare earth complexes were blended with silicon rubber over the melting point of Eu （TTA） 2 （phen） （MA）. Next, a definite amount of 2,5-dimethyl-2, 5-di （tert-butylperoxy） hexane was added as a cross linker to the composite, to get the uncured composites. Subsequently, the composites were vulcanized at 160℃, and silicon rubber-based composites with different contents of the complexes were prepared and their fluorescent properties were observed. The contents of rare earth complexes were 0.96 %, 2.83 %, 4.63 % and 6.36 % （mass fraction）, respectively. Moreover, the composites of Eu （TTA） 2 （phen） （ MA ）/SiR were measured by SEM, XRD, and fluorescent spectra. The measurement result shows that the fluorescent intensity of uncured rubber is similar to one of the pure rare earth complexes. However, there is no marked change of fluorescent intensity in the uncured rubber when the content of rare earth complexes continues to increase.

Spectroscopic Characterization of Eu-Enoxacin-Phen Complexes and Determination of ATP by Fluorescence Quenching

The complex of Eu 3+ and Enoxacin(ENX) and Phen was synthesized. Its compositions is Eu(ENX)_3(phen)Cl_3·2H_2O. Its fluorescence spectra were studied. The results show that the strong fluorescence emitting of 592 and 616 nm for Eu 3+ in the Eu(ENX)_3(phen)Cl_3·2H_2O complex is related to the transitions 5D_0-7F_1 and 5D_0-7F_2 respectively. A sensitive method for the determination of adenosine triphosphate(ATP) by fluorescence quenching is proposed. The method is based on the ability of ATP to inhibit the formation of a strong fluorescent complex of Eu(ENX)_3(phen)Cl_3·2H_2O. In conditions of pH 6.7 in HAc-NaAc buffer and λ_ ex=340 nm and λ_ em=616 nm, the linear range of the determination is 0.4～ 10 μg·ml -1 and the detection limit is 0.034 μg·ml -1 for ATP. The method was applied to determine ATP in adenosine disodium triphosphate injection samples with relative standard deviation of 212% and recovery of 94.8%～1037%.