Luminescence of Terbium Complexes Incorporated into Silica Matrix

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Synthesis, Characterization and Fluorescence Properties of Europium, Terbium Complexes with Biphenyl-4-Carboxylic Acid and o-Phenanthroline

Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indicate that the complexes have the composition of Eu(phen)L3·1/2H2O, Eu0.5RE0.5(phen)L3·1/2H2O; Tb(phen)L3·H2O and Tb0.5RE0.5(Phen)L3·1/2H2O. (RE=Y3 , La3 and Gd3 ; L=biphenyl 4-carboxylic acid; phen=o-Phenanthroline). The studies of their IR, UV 1H NMR and molar conductivities demonstrate that biphenyl 4-carboylic acid is bounded with RE(Ⅲ) ion. Rare earth ions coordinate with two nitrogen atoms of phen molecules directly in these rare earth complexes. The fluorescence spectra and fluorescence lifetimes of the rare earth complexes show that the fluorescent intensity and lifetime of a series of europium complexes are longer than those of the series of terbium complexes as having the some ligands. There are better fluorescent intensity and lifetime of hetero-nuclear rare earth complexes than homo-nuclear rare earth complexes for europium complexes. The fluorescence emission intensity of Eu3 is raised by inert fluorescent rare earth ions (Y3 , Gd3 and La3 ), but in Tb3 hetero-nuclear rare earth complexes the intensity of Tb3 ions are quenched by the inert fluorescent rare earth ions.     

A series of rare earth coordination polymer constructed from paddle-wheel building blocks

Three coordination polymers, Ln2（bpdc）3（phen）2（H2O）2 （Ln=Nd（1）, Eu（2）, and Tb （3）; bpdc=2,2＇-bipyridine-3,3＇-dicarboxylate; phen=1,10-phenanthroline）, were obtained by hydrothermal reaction of Ln2O3 with 2,2＇-bipyridine-3,3＇-dicarboxylate acid, and 1,10-phe- nanthroline. They were characterized by single-crystal X-ray diffraction, IR spectra, and photoluminescent spectra. The crystallographic data of 1-3 indicated that they were isostructural. Both complexes contained paddle-wheel building blocks, formed by bpdc and phen ligands. These paddle-wheel secondary building units （SBUs） were further connected to form two-dimensional （2-D） metal organic framework （MOF） networks by 2,2＇-bipyridine-3, and 3＇-dicarboxylate tinkers. A three-dimensional （3-D） supramolecular structure was formed by π-π aromatic interactions between adjacent 2-D infinite networks. Photoluminescent measurements indicated that europium compound 2 and terbium compound 3 were strong, red and green emitters, respectively.     

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-phenanthroline, 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 room 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.     

Thermal Stability and Luminescence Properties of Eu^3＋ and Tb^3＋ Complexes with a Silica Matrix by Sol-Gel Method

Ternary complexes of europium and terbium with benzoic acid and 1, 10-phenanthroline [RE(BA)3phen] (BA=benzoate phen=1,10-phenanthroline) were introduced into a silica matrix by sol-gel method. The thermal stability and luminescence behavior of the complexes in silica gels were studied in comparison with the corresponding solid-state complexes by thermal decomposition, excitation and emission spectra. The thermal stability of the complexes is enhanced in silica gel matrix and the luminescence remaines unchanged.     

Synthesis and characterization of terbium（Ⅲ）-pyromellitic acid（H4L）-1,10-phenanthroline （phen） luminescent complex

The terbium(Ⅲ)-pyromellitic acid(H4L)-1,10-phenanthroline(phen) luminescent complex was synthesized using a co-precipitation method.The chemical composition of the synthesized complex was speculated to be Tb4L3(phen)0.075·10H2O by elemental analysis,inductively coupled plasma-atomic emission spectroscopy(ICP-AES),and Fourier-transform infrared spectroscopy(FT-IR).The X-ray diffraction analytic results indicated that the synthesized complex is a new crystalline complex,whose structure was different from those of other two ligands.The scanning electron microscopy analytic results showed that the product was of spherical crystals with good dispersion property,and the mean diameter of the spheres was about 1-2 μm.The TG-DTA result showed that the complex had good stability below 489 °C.PL spectra showed that the complex emitted characteristic green fluorescence of Tb(Ⅲ) ion under ultraviolet excitation.     

Influence of La, Y, Gd, Cu, NH4^＋ Ions and DMSO on Luminescent Property of Terbium Complexes with Sulfosalicylate

Ｔｈｅｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｏｆｏｒｇａｎｉｃｌｉｇ ａｎｄｓａｓｆｌｕｏｒｅｓｃｅｎｔｍａｔｅｒｉａｌｓｈａｖｅｒｅｃｅｉｖｅｄｅｘ ｔｅｎｓｉｖｅａｔｔｅｎｔｉｏｎ .Ｔｈｅｕｓｅｏｆｆｌｕｏｒｅｓｃｅｎｔｏｒｇａｎｏ ｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｒｅｑｕｉｒｅｈｉｇｈｆｌｕｏ ｒｅｓｃｅｎｃｅｉｎｔｅｎｓｉｔｙａｎｄｌｏｗｃｏｓｔｃｏｍｐｌｅｘｅｓ .Ｉｎｒｅｃｅｎｔｙｅａｒｓ ,ｔｈｅｆｌｕｏｒｅｓｃｅｎｃｅｅｎｈａｎｃｅｍｅｎｔｏｆＴｂ(Ⅲ )ｏｒＥｕ(Ⅲ )ｃｏｍｐｌｅｘｅ…     

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

Eu3 ,Tb3 canemitfluorescenceinconjugatedsystemcontainingorganicligand[1,2 ] ,forexample ,1 ,1 0 phenanthroline ,becauseithasbettercoordina tionabilityandbiggerconjugationsystem ,soitcantransmitenergyeffectivelytoEu3 ,Tb3 ,leadingtofluorescenceemission ,andthestabilityisveryhigh ,butsolubilityisverypoor .Inaddition ,diphenylsul foxidehasbettercoordinationabilityandbiggerconju gationsystem ,too .Soitcanalsotransmitenergyef fectivelytoEu3 ,Tb3 ,resutlinginfluorescencee mission ,andsolubi…     

Triboluminescence of A New Europate Complex

A new europium (Ⅲ)complex Eu(HFNH)3Phen (HFNH: 4, 4, 5, 5, 6, 6, 6-heptafluoro-l-(2-naphthyl)hexane-1,3-dione ; phen : 1, 10-phenanthroline) was synthesized and its tribolumineseent phenomenon was observed. Photoluminescence and tfiboluminescence spectra were successfidly determined. The most intense tfiboluminescent emission originates from the transition of the central Eu^3 ion from ^5D0 level to ^7F2 level. The tribolunlinescent spectrum is basically similar to that of photoluminescence, which correlates with the disorders of F atoms.     

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 diffrac-tion analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group P-1. Both are binuclear molecules with an inversion center. In complex 1, two center Eu3+ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu3+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 Eu3+ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu3+ 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 Eu3+ ion were observed in their emission spectra.     

Synthesis and Luminescence of Complexes EuxY1-x（phen）L3

A series of binuclear complexes with different molar ratio of europium to yttrium with cinnamic acid and o-phenanthroline were synthesized in anhydrous alcohol. Elemental analysis shows that the composition of the complexes areEuxY1-x(phen)L3(L: C6H5CH=CHCOO, x = 1.0, 0.7, 0.5, 0.3 and 0.1). The IR absorption spectra indicate that cinnamate is coordinated to the rare earth ions and chemical bonds are formed between rare earth ions and nitrogen atoms of o-phenanthroline. Fluorescent spectra show that the emission of Eu^3 ion can be greatly enhanced if some of europium ions in the complexes are substituted by yttrium ions.     

Hydrothermal synthesis, crystal structure and luminescence of a europium complex with phenylmalonic acid and 1, 10-phenanthroline

A new complex Eu2（PA）6（phen）2 was prepared with hydrothermal reaction using EuCl3.6H2O, phenylmalonic acid （H2phma）, and 1, 10-phenanthroline （phen）, where PA was the decarboxylated product of HEphma, phenylacetate. The crystal structure of the title complex was determined with the X-ray diffraction. The title complex was a binuclear molecule with an inversion center. Each Eu^3＋ ion was nine-coordinated with two nitrogen atoms from one phen molecule and seven oxygen atoms from five PA ligands. The carboxylic groups were bonded to the Eu^3＋ ion in three modes, the chelating bidentate, the bridging bidentate, and the bridging-chelating tridentate. The complex emits intense red fluorescence under ultraviolet light. The luminescence peaks correspond to the characteristic emission 5D0→7FJ （J=0-4） transitions of the Eu^3＋ ion.     

Thermochemical studies on complex of [Sm(o-NBA)_3phen]_2

A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔθ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle according to Hess’s Law, the standard molar enthalpy of formation of [Sm(o-NBA)3 phen]2 (s) was estimated to be f mHΔθ=–4109.2±7.3 kJ/mol.     

Synthesis and crystal structure of a novel double 1：11 series arsenotungstate： [Cu^I（phen）2]5H6[Sm（AsW11O39）2]·6H2O

A novel double 1：11 series arsenotungstate, [Cu^I（phen）2]5H6[Sm（AsW11O39）2]·6H2O （phen=1, 10-phenanthroline） was synthesized by the hydrothermal method and characterized by elemental analysis, 1R spectra, and single-crystal X-ray diffraction. The title compound was monoclinic, space group P2 1/c, a=3.75710（2） nm, b=1.39776（8） nm, c=-3.33735（18） nm, β=96.967（10）°, V=17.3969（17） nm^3, Z=4. Single crystal X-ray structural analyses revealed that the dimeric polyanion, [SmAs2W22O78]^1-, consisted of one central Sm^3＋ ion and two tetradentate heteropoly ligands [ASW11O39]^7-. The Sm^3＋ ion and two tetradentate defective [AsW11O39]^7- anions were joined together by the sharing of four oxygen atoms from each heteropoly ligand. The bond valence sum （BVS） calculations of the title compound suggested that all four Cu atoms were in the ＋1 oxidation sate.     

Synthesis and crystal structures of La(Ⅲ),Y(Ⅲ) complexes of homoveratric acid with 1,10-phenanthroline

Two three-dimensional complexes Ln(DMPA)3phen2(HDMPA=3,4-dimet hoxyphenylacetic acid,homoveratric acid;Ln=La,Y;phen=1,10-phenanthroline) were synthesized under hydrothermal conditions and characterized with IR and emission spectra.The crystal structures were determined with single crystal X-ray diffraction method.The two compounds were isostructural,and 3D supramolecule architectures were formed by hydrogen bonds and π-π stacking interactions.They strongly emitted upon excitation due to π→π transition of the ligands.     

Synthesis and Photoluminescence of Three Europium (Ⅲ) Ternary Complexes with New Secondary Ligands of Different Structure

Three new 1,10-phenanthroline derivatives, dipyrido (3,2-f: 2,3-h) quinoxaline (DPQN), imidazo (5,6-f)-(1,10)-phenanthroline (IP) and 3-phenyl-imidazo (5,6-f)-(1,10)-phenanthroline (PIP) were designed and synthesized as a secondary ligand to coordinate with europium (Ⅲ) ion while dibenzoylmethane (DBM) was used as the first ligand. The compositions of the ligands and the europium (Ⅲ) ternary complexes were confirmed by elementary analysis, IR and 1H-NMR spectroscopy. The UV-visible absorption spectra, thermal stability, photoluminescence spectra, quantum yield and fluorescence life time of the Eu(Ⅲ) complexes were investigated. The effect of the structure of the secondary ligand on the photoluminescence of the complexes was discussed. The results show that the synthesized Eu(Ⅲ) complexes are good red-emitiing materials for potential application in fabrication of organic electroluminescence devices.     

Emission Characteristics of PVK Doped TbY（o-MBA）6（phen）2 Systems

Since the pioneering work of Tang and VanSlykeon organic light emitting diodes(OLEDs)in1987,OLEDs have been particularlyinterestedin because oftheir potential applications in next-generationflat-pan-el displays and large-area flexible displays[1~3].Rareearth complex materials have been widely used incathodoluminescent display phosphor screens,lasersand lamps because their photoluminescence PL ex-hibits high quantumefficiencies and very sharp spec-tral bands.Inthe1990s,Kido et al[4~6]first…     

Luminescence properties of polymers containing europium complexes with 4-tert-butylbenzoic acid

The binary europium complex EuL3 (L=4-tert-butylbenzoate) and ternary europium complexes EuL3TTA0.1 (TTA=2-thenoyltrifluoroacetone), EuL3DBM0.5 (DBM=dibenzoylmethane) and EuL3phen0.5 (phen=1, 10-phenan...     

Synthesis, Structure and Luminescent Properties of a Nine-Coordinated Praseodymium Complex

The Pr (TFA) 3phen ( C2H5OH ) quarternary complex with 2-thenoyhrifluoro-acetone ( TFA ), 1,10phenanthroline(phen) and ethanol were synthesized and characterized by single-crystal X-ray diffraction. The central Pr^3 ion is nine-coordinated. The infrared (IR)spectrum, diffuse reflectance (DR)spectrum and fluorescence measurements of the complex were investigated.     

Organic Light Emitting Devices Based on Terbium Complex

Rare earth complex TbY(m-MOBA)6(phen)2·2H2O was synthesized,which was first used as an emitting material in electroluminescence.The properties of monolayer device with the rate of 1000 r·min-1 (70 nm) and the impure concentration of 1∶5 were the best.And the highest brightness of this device reached 21.8 cd·cm-2 at a fixed bias of 20 V.Bright green emission can be obtained from the optimized double-layer device,and the highest EL brightness of the device reached 289 cd·m-2 at the voltage of 21 V.