Synthesis and luminescence properties of rare earth ternary complexes consisting of Eu(III), β-diketones and 1,10-phenanthroline

Three novel β-diketones (HPPP, HTPP, and HFPP) ligands were synthesized by Sonogashira coupling reaction and Claisen con- densation. The structure of β-diketones was confirmed with elemental analysis, IR, NMR and MS spectra. Three new ternary complexes consisting of Eu(III), β-diketones, and 1,10-phenanthroline(phen) were synthesized and characterized as TbL3phen (L=PPP, TPP, FPP) with elemental analysis, chemical analysis, and IR spectra, and their luminescence properties were studied.     

Synthesis, EPR and Fluorescence Properties of Quaternary Lanthanide Complexes with Chloroacetate and Phenanthroline Ligands

A series of novel quaternary mixed anion complexes of lanthanide containing 1, 10-phenanthroline (phen) and chloroacetate ligands were synthesized from the water/ethanol solution with slightly acidic solution and characterized by elemental analysis, IR, UV and thermal analysis. The EPR and fluorescence properties also were studied.     

Synthesis,Characterization and Thermal Decomposition Behaviour of Tri-aquo Lanthanum(Ⅲ)Malonate Bimalonate

A new complex of malonic acid with lanthanum,La(Hmal)·(mal)·3H_2O,was synthesizedand characterized by elemental analysis and IR spectra.The thermal decomposition process and their kineticparameters n and E_a were studied by means of TG and DTG.All of the intermediate and end productswere determined and characterized by the mass loss in TG curve,elemental analysis and IR spectra.     

Synthesis and fluorescence properties of Eu（Ⅲ）, Tb（Ⅲ） and Sm（Ⅲ） with β-diketone and 2,2＇- bipyridine

Three new rare earth ternary complexes,RE(PPP)3bpy(RE=Sm 3+ ,Eu 3+ ,Tb 3+ ),were synthesized by the reaction of 1-phenyl-3-(p-phenylethynylphenyl)-1,3-propanedione(HPPP)and 2,2′-bipyridine(bpy)with rare earth chloride RECl3,respectively,in alcohol solution. The compositions were characterized by means of infrared(IR)spectra,chemical analysis,elemental analysis,and thermodynamic analysis.Luminescent properties of the three complexes were studied.At room temperature,under UV light excitation,the Sm 3+ ,Eu 3+ and Tb 3+ complexes exhibited characteristic emission of the central ions.The fluorescence spectra showed that the fluorescence emission intensity of Eu 3+ complex was the strongest.The narrow strongest emission band of Eu 3+ complex was considered to be a valuable material with bright red fluorescence.     

Synthesis and Characteristic Study on Complexes of Europium（Ⅲ） and Maleic Acid Doped with Non-Fluorescent Ions

Complex of europium （Ⅲ） with maleic acid, and binuclear complexes of europium（Ⅲ）with maleic acid doped with non-fluorescent ions gadolinium, lanthanum and yttrium, were synthesized. The compositions and structures of complexes were characterized with elemental analysis, single crystal X-ray diffraction, IR and DSC-TG. Fluorescent properties were studied with fluorescence spectrum. The results indicated that the strongest fluorescent complexes were obtained when the ratio of europium and non-fluorescent ion was 8：2. The order of Eu^3＋ fluorescence strengthened by three doped rare earths was Gd^3＋ 〉La^3＋ 〉Y^3＋     

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.     

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.     

On the Rare Earth Chelates of(1'-Phenyl-3'-Methyl-5'-Pyrazolone-4')-Carbonylmethanoic Acid and 1,10-Phenanthroline

Some rare earth chelates of(1'-phenyl-3'-methyl-5'-phrazolone-4')-carbonylmethanoic acid and 1,10-phenanthroline have been synthesized.The composition of the complexes were confirmed by elemental analy.sis.The molar conductance,IR,~4H-NMR,electronic spectra and thermogravimetric analysis of the chelateshave been measured and discussed.     

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.     

Synthesis and Characterization of Complexes of Rare Earth Nitrates with N, N -Bis（3-pyridylmethyl） -1,2-ethylenediamine

In this paper, a series of complexes of rare earth nitrates with N, N‘-bis(3-pyridylmethyl)-1,2-ethylenediamine ligand (L) were synthesized from the acetonitrile solution. The obtained new complexes were characterized by elemental analysis, IR spectroscopy and thermogravimetric analysis. The results showthat all the complexes have l: 1 molar ratio of metal,     

Synthesis and luminescence properties of rare earth ternary complexes consisting of Eu(Ⅲ), β-diketones and 1,10-phenanthroline

Three novel β-diketones (HPPP, HTPP, and HFPP) ligands were synthesized by Sonogashira coupling reaction and Claisen con-densation. The structure of β-diketones was confirmed with elemental analysis, IR, NMR and MS spectra. Three new ternary complexes consisting of Eu(Ⅲ), β-diketones, and 1,10-phenanthroline(phen) were synthesized and characterized as ThL3phen (L=PPP, TPP, FPP) with elemental analysis, chemical analysis, and IR spectra, and their luminescence properties were studied.     

Thermochemical Properties of the Complexes RE(HSal)3·2H2O(RE = La, Ce, Pr, Nd, Sm)

Five solid rare earth salicylate complexes were synthesized by low hydrated lathanide chloride and salicylic acid. The complexes in this experiment were identified as the general formula RE(HSal)₃·2H₂O(RE = La, Ce, Pr, Nd, Sm) by elemental analysis and EDTA volumetric analysis. IR spectra of the complexes show that carboxyl of salicylic acid coordinates to RE³⁺ ions. Electrochemical behaviors of the complexes on the glass-carbon electrode were researched with cyclic voltammetry (CV). It is indicated that the electrochemical process of the complexes is a one-electron redox process and the electrochemical reversibility of complexes is less than that of the lanthanide chlorides. The constant-volume combustion energies of complexes, Δ_cU, were determined with a precise rotating-bomb calorimeter at 298.15 K. Their standard molar enthalpies of combustion, Δ_cH_m^θ, and standard molar enthalpies of formation, Δ_fH_m^θ, were calculated.     

稀土铕,铽β-二酮配合物的合成与发光性能

采用Claisen缩合反应合成了一种新型的β-二酮化合物1-(4-溴苯)-3-苯基丙烷-1,3-二酮(L),并以其为第一配体,邻菲罗啉(phen)为第二配体,合成出新型稀土铕,铽二元及三元配合物。通过元素分析、红外光谱、紫外光谱、荧光光谱对合成的配体及配合物进行了表征。元素分析确定了配合物的组成。红外光谱的分析表明第一配体L中的氧原子以及第二配体phen中的氮原子与稀土离子进行了配位。紫外光谱表明第一配体L为能量的给体,第二配体phen起协同作用。通过荧光光谱研究了配合物的发光性质,结果显示三元配合物的发光强度大于二元配合物,三元配合物Eu(L)3phen表现出Eu3+的特征发射,在593,615,653,701 nm处的发射峰分别归属于Eu3+的5D0→7Fj(j=1,2,3,4)能级间的跃迁,并且以位于615 nm处的5D0→7F2电子跃迁所发出的荧光强度最大;而铽配合物中并没有出现Tb3+的特征发射。进一步的研究表明,这是由于配体L的最低三重态能级较适合Eu3+的发射能级,配体L吸收的能量可以有效的通过Antenna效应传递给稀土中心离子,使得三元配合物Eu(L)3phen的发光强度较大。     

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

Two three-dimensional complexes [Ln(DMPA)₃phen]₂ (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, 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.     

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.     

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 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.     

Fluorescence and Judd-Ofelt analysis of rare earth complexes with maleic anhydride and acrylic acid

Two kinds of Eu-complexes, Eu(TTA)2(Phen)(AA) and Eu(TTA)2(Phen)(MA) (HTTA=2-Thenoyltrifluoroacetone, Phen=1,10- phenanthroline, AA=acrylic acid, MA=Maleic anhydride), which combined the excellent fluorescence properties of Eu(TTA)2(Phen)(H2O) and the reactivity of acrylic acid and maleic anhydride with radicals, were synthesized. The two complexes were characterized by elemental analysis, infrared (IR) spectra, and X-ray photoelectron spectroscopy (XPS). Based on the data shown from the fluorescent spectra of the Eu-MA and Eu-AA complexes, the ?λ (λ=2 and 4) experimental intensity parameters were calculated. The results demonstrated that the ?2 intensity parameters for the two complexes were smaller than those for the Eu(TTA)2(Phen)(H2O) complex, indicating that a less symmetri- cal chemical environment existed in the complexes. It implied that the radiative efficiency of the 5D0 of these two complexes could be en- hanced by ligand of MA and AA, respectively. The luminescent lifetime of the Eu-AA (τ=7.26×10–4 s) or Eu-MA complex (τ=8.12×10–4 s) was higher than that of the Eu(TTA)2(Phen)(H2O) complex, which was attributed to the substitution of the water molecule (H2O) in Eu(TTA)2(Phen)(H2O) by the MA or AA ligand.