Synthesis and Characterization of Lanthanide Complexes Involving Cyclopentadienyl and Benzohydroximic Acid Ligand

Ｉｎｇｅｎｅｒａｌ,ｈｙｄｒｏｘｉｍｉｃａｃｉｄｓ (ＲＣＯＮ ＨＯＨ)ａｒｅｗｅａｋｏｒｇａｎｉｃａｃｉｄｓ .ＴｈｉｓｃｌａｓｓｏｆｏｒｇａｎｉｃｃｏｍｐｏｕｎｄｓｃｏｎｔａｉｎｉｎｇｔｈｅｒｅａｃｔｉｖｅｇｒｏｕｐＣＯＮＨＯＨ ,ｋｎｏｗｎａｓｔｈｅｈｙｄｒｏｘｉｍｉｃａｃｉｄｓ,ｈａｖｅｂｅｅｎｗｉｄｅｌｙｓｔｕｄｉｅｄｂｙｏｒｇａｎｉｃｃｈｅｍｉｓｔｓ.Ｔｈｅｈｙｄｒｏｘｉｍｉｃａｃｉｄｓａｒｅｃｈｅｌａｔｅｌｉｇａｎｄｓｆｏｒｍａｎｙｍｅｔａｌｓ .Ｔｈｅｙａｒｅｗｉｄｅｌｙｕｓｅｄａｓｃｈｅｌ…     

Crystal Structure and Luminescence Property of Lanthanide Complexes with 2-Fluorobenzoic Acid and 2,2′-Bipyridine

Lanthanidemixed ligandscarboxylatecomplexes containing2,2′bipyridineor1,10phenanthrolinehavebeenwidelystudied[1～12],becausethesecom plexesexhibitvariouskindsofstructuraltypes,high stabilityandintensefluorescencecharacter.Inpartic ular,europiumcomplexeso…     

Synthesis, Characterization and Crystal Structure of Neutral Homoleptic Lanthanide Amide Yb（NPh2）3（THF）2

A neutral homoleptic lanthanide amide Yb(NPh2)3(THF)2 was obtained by reaction of anhydrous YbCl3 with LiNPh2 in THF. The product was characterized by elemental analysis, infrared spectrum and X-ray crystallographic analysis. The crystal data are monoclinic, P21/n space group, a=1.2052(2) nm, b=1.9369(3) nm, c=1.6523(2) nm, β=92.79(1)°, V=3.8524(9) nm3, Z=4, Dc=1.417 g*cm-3, μ=24.67 cm-1 (Mo Kα), F(000)=1668, R=0.036, Rw=0.039. The central metal ytterbium is coordinated by three terminal NPh2 groups and two THF molecules to form a five-coordinate distorted trigonal bipyramid. The mean Yb-N bond length is 0.2219(6) nm.     

Synthesis, Characterization and Crystal Structure of Neutral Homoleptic Lanthanide Amide Yb(NPh_2)_3(THF)

Ｌａｎｔｈａｎｉｄｅａｍｉｄｅｃｏｍｐｌｅｘｅｓａｒｅａｎｉｍ ｐｏｒｔａｎｔｃｌａｓｓｏｆｐｒｅｃｕｒｓｏｒｓｆｏｒｌａｎｔｈａｎｉｄｅｄｅｒｉｖａｔｉｖｅｓ .Ｉｔｃａｎｂｅｅａｓｉｌｙｔｒａｎｓｆｏｒｍｅｄｔｏｃｏｒ ｒｅｓｐｏｎｄｉｎｇｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｂｙｒｅａｃｔｉｎｇｗｉｔｈｉｎｖｏｌｖｉｎｇｐｒｏｔｉｃｒｅａｇｅｎｔｓ[1,2 ] .Ｔｈｅｌａｎｔｈａｎｉｄｅａｍｉｄｅｕｓｅｄａｓｓｙｎｔｈｅｔｉｃｐｒｅｃｕｒｓｏｒｉｓｎｅｕｔｒａｌｈｏｍｏｌｅｐｔｉｃｃｏｍｐｌｅｘ ,ｏｔｈ…     

Synthesis, Characterization and Properties of Lanthanide Nitrate Complexes with Isonicotinoyl Hydrazone

Ｔｈｅｄｅｓｉｇｎａｎｄｓｙｎｔｈｅｓｉｓｏｆｓｔａｂｌｅｌａｎ ｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓａｒｅｏｆｇｒｅａｔｉｍｐｏｒｔａｎｃｅｆｏｒｔｈｅｉｎｖｅｓｔｉｇａｔｉｏｎｏｆｔｈｅｐｒｏｐｅｒｔｉｅｓａｎｄａｐｐｌｉｃａ ｔｉｏｎｓｏｆｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓ .Ｍａｃｒｏｃｙｃｌｉｃｏｒａｃｙｃｌｉｃｌｉｇａｎｄｓｗｉｔｈｍｕｌｔｉｄｅｎｔａｔｅｄｏｎｏｒａｔｏｍｓｕｓｕａｌｌｙｆｏｒｍｓｔａｂｌｅｃｏｍｐｌｅｘｅｓｗｉｔｈｌａｎｔｈａｎｉｄｅｃａｔｉｏｎｓ .Ｔｈｅｓｉｚｅｏｆ…     

Hydrothermal syntheses and characterization of three lanthanide coordination complexes constructed by 2,2’:6’,2’’-terpyridine and 2,2’-biphenyldicarboxylic acid

Two 1D coordination polymers [Ln2(dpdc)3(tpy)2·H2O]n [Ln=Nd 1, Yb 2, H2dpdc=2,2’-biphenyldicarboxylic acid and tpy= 2,2’:6’,2’’-terpyridine] and one dinuclear complex Er2(dpdc)2(Hdpdc)2(tpy)2 3 were obtained via hydrothermal reactions and determined by X-ray diffraction analysis. The crystal structure data of 1 and 2 revealed that two coordination polymers were isostructural and possessed a 1D chain framework consisting of eight-coordinated Ln(III) centers. In the asymmetric unit, the two Er(III) ions in 3 were both nine-coordinated and had similar coordination environments. The Er(III) ions were bridged by dpdc2-ligands into dinuclear structures. The complexes were also characterized by IR spectra and thermogravimetric analysis. The solid fluorescence of 1 and 3 was also investigated at room temperature.     

Structure of Complexes of Lanthanides with N,N''-Dimethyl-3-Oxa-Glutaramic Acid

A new stripping agent N,N-dimethyl-3-oxa-glutaramic Acid (DOGA) was used in TRPO process to simplify the TRPO process. The structures of the complexes of the DOGA with Eu(Ⅲ), Nd(Ⅲ), La(Ⅲ) were characterized with extended X-ray absorption fine structure spectroscopy (EXAFS), infrared spectra (IR) and mass spectra (MS). The molecular formula of the complexes of Eu(Ⅲ) and Nd(Ⅲ) is deduced to be M(DOGA)3, and only La(Ⅲ) can form the complex HM(DOGA)4 under condition of high consistency of the DOGA. The coordination number of Ln(Ⅲ) in the complexes is 8, and all of coordinated donor atoms are O atoms. For Eu(Ⅲ), Nd(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of Ln-O are 0.240 nm, 0.244 nm respectively, while the numbers of the second O shell are 2.4, and the average coordination bond lengths of Ln-O are 0.260 nm, 0.262 nm. For La(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of La-O are 0.258 nm, while the number of O atom in the second coordination shell is 4.4, and the average coordination bond length of La-O is 0.28 nm. The results of IR and MS show that there is no water coordinating with Ln(Ⅲ) in the complexes.     

Synthesis and Application of Lanthanide Complexes with Schiff Base of Pridoxylidence-Glycine

Ｔｈｅｈａｒｍｆｕｌｎｅｓｓｏｆｈｅａｖｙｍｅｔａｌｅｌｅｍｅｎｔｓｏｎｐｌａｎｔｓｉｓｏｎｅｏｆｔｈｅｓｅｒｉｏｕｓｅｎｖｉｒｏｎｍｅｎｔａｌｐｒｏｂｌｅｍｓｏｆｔｈｅｍｏｄｅｒｎｗｏｒｌｄ .Ｉｎｒｅｃｅｎｔｙｅａｒｓ ,ｔｈｅｓｔｕｄｙｏｎｔｈｅｍｉｓａｌｓｏｏｎｅｏｆｖｅｒｙａｃ ｔｉｖｅｒｅｓｅａｒｃｈｐｒｏｊｅｃｔｓｉｎｐｌａｎｔｐｏｌｌｕｔｉｏｎｅｃｏｌｏｇｙｆｉｅｌｄｓ[1～ 6 ] .ＬａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｗｉｔｈｔｈｅＳｃｈｉｆｆｂａｓｅａｒｅａｃｌａｓｓｏｆｃｏｍｐｏｕ…     

Standard Enthalpies of Formation of Solid Complexes of Lanthanide Nitrates with Alanine

Ｇｒｅａｔｉｎｔｅｒｅｓｔｈａｓｂｅｅｎａｒｏｕｓｅｄｉｎｔｈｅｓｔｕｄｙｏｆｃｏｍｐｌｅｘｅｓｏｆｒａｒｅｅａｒｔｈｓａｌｔｓｗｉｔｈａｍｉｎｏａｃｉｄｓｂｅｃａｕｓｅｒａｒｅｅａｒｔｈｉｏｎｓｐｏｓｓｅｓｓｓｏｍｅｓｐｅｃｉａｌｆｕｎｃｔｉｏｎｓｉｎｂｉｏｃｈｅｍｉｓｔｒｙ .Ｔｈｅｙｃａｎｂｅｕｓｅｄａｓａｐｒｏｂｅｔｏｌａｂｅｌｔｈｅｃａｌｃｉｕｍｉｏｎ .Ｍｏｒｅｏｖｅｒ,ａｍｉｎｏａｃｉｄｓａｒｅｔｈｅｓｔｒｕｃｔｕｒｅｕｎｉｔｏｆｐｒｏｔｅｉｎｓ .Ｇａｏａｎｄｃｏｗｏｒｋｅｒｓｒｅｃｅ…     

Syntheses of Alkaline Earth and Lanthanide Cryptates with Pyridine-Based Group

New alkaline earth metal cryptates [ML]（NO3）2 ·2H2O （M=Ca^2＋, Sr^2＋, Ba^2＋; L = 1, 4,12,15,18, 26, 31, 39, 42, 43, 44-undecaazapentacyclo- [ 13.13.13.1^6,10 .1^20,24 .1^33,37 ]-tetratetraconta -4, 6, 8, 10（44）, 11, 18, 20, 22, 24（43）, 25, 31, 33, 35, 37（42）, 38-pentadecaene） were synthesized by [2 ＋ 3 ] template condensation of tris（2-aminoethyl） amine with 2, 6-diformylpyridine, and then by transmetallation reactions of the calcium cryptate [CaL] （NO3）2·2H2O with corresponding lanthanide ions; three lanthanide cryptates [ LnL] （NO）3·3H2O （Ln = Eu, Gd, Tb） were synthesized and characterized by physical methods. The crystal structure of the terbium cryptate [TbL] （NO）3·3H2O was studied by X-ray analysis. The central atom was coordinated by three pyridyl and six imino nitrogen atoms and exhibited a distorted tricapped trigonal prismatic coordination geometry.     

La(Ⅲ)、Nd(Ⅲ)、Tb(Ⅲ)、Er(Ⅲ)与二溴水杨醛缩乙二胺配合物的合成与表征及薄层色谱研究

合成了四种稀土双核配合物,其组成为Ｌｎ２Ｌ３（ＮＯ３）６·３Ｈ２Ｏ〔Ｌｎ＝Ｌａ（Ⅲ）、Ｎｄ（Ⅲ）、Ｔｂ（Ⅲ）、Ｅｒ（Ⅲ）;Ｌ＝３,５－二溴水杨醛缩乙二胺〕,并通过元素分析、红外光谱、紫外光谱、差热－热重及摩尔电导分析等手段,对合成的配合物进行了表征,并研究了配合物的薄层色谱行为     

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 and Photophysical Properties of Dy^3＋ and Gd^3＋ Polymeric Complexes with Functionalized Polybenzimidazole Containing β-Diketone Side Group

The polymeric ligand PBIa （functionalized polybenzimidazole containing β-diketone side group） was successfully synthesized via the reaction of polybenzimidazole （PBI） with 3-Br-acetylacetone in DM SO solvent using Nail as the deprotonation reagent. Its corresponding polymeric complexes of Dy^3＋ and Gd^3＋ were prepared and characterized by FT-IR, ^1H NMR, molar conductance measurements, and thermal analysis. The photoluminescence properties and the probable mechanism of the Dy and Gd complexes were studied. The measurement and analysis of the thermal properties showed that these were thermal stable.     

邻菲罗啉和水杨酸与RE(Ⅲ)三元配合物的合成及表征

在无水甲醇中合成了邻菲罗啉 ( Phen)、水杨酸 ( HSal)与 Nd( )、Sm( )的固态三元配合物。研究了其化学组成、溶解性、红外光谱和摩尔电导等性质 ,证实配合物的化学组成式为 Nd( Phen) 2 ( Sal) 2 Cl· H2 O及 Sm( Phen) 2 ( Sal) 2 Cl· H2 O,金属离子的配位数为 9。     

Synthesis, crystal structure and fluorescence of a new europium complex with 2-bromobenzoate and 2,2′-bipyridine

A new complex of {[Eu2(2-BrBA)6(2,2'-bpy)2]2.CH3CH2OH·H2O} (2-BrBA=2-bromobenzoate; 2,2'-bpy=2,2'-bipyridine) was prepared by solvent method and characterized with X-ray single-crystal diffraction, IR spectroscopy, UV spectrscopy, and fluorescence spectroscopy. The complex crystallized in triclinic crystal system, PT space group, with a=1.17196(4) nm, b=-2.36142(9) nm, c=2.59151(9) nm, a=113.266(2)°, β=101.100(2)°, and γ=94.400(2)°. Two independent dinuclear molecules were contained in the asymmetric unit. The two molecules were similar to each other. Each Eu(Ⅲ) ion was nine-coordinated with seven oxygen atoms from five 2-BrBA ligands and two ni-trogen atoms from 2,2'-bpy molecule. The carboxylate groups acted as bidentate-chelating, bidentate-bridging and chelating-bridging coor-dination modes. The complex adopted a distorted monocapped square-antiprism coordination geometry. Five peaks at 579, 591, 613, 652,and 697 nm appeared in the fluorescence spectrum, corresponding to 5D0→7F0, 5D0→7F1, 5D0→7F2, 5D0→7F3, and 5D0→7F4 transition emis-sions of the Eu(Ⅲ) ion, respectively.     

Luminescence properties of the co-luminescence groups of Sm-La-pyridyl carboxylic acids

A novel ligand, N,N’-(2,6-pyridinedicarbonyl)bis[N-(carboxymethyl)] (L1) was designed and synthesized starting from pyri-dine-2,6-dicarboxylic acid (1). The ligand (L1) and intermediate product (3) were characterized by 1H nuclear magnetic resonance (NMR), Fourier transform infrared spectrometer (FT-IR) spectra and elemental analysis. Besides, four novel co-luminescence systems of Sm-La-pyridyl carboxylic acids: K4Sm(1-x)Lax(L1)Cl3·y1H2O, K12Sm2(1-x)La2x(L2)3 Cl6·y2H2O, K6Sm2(1-x)La2x(L3)Cl6·y3H2O and K4Sm(1-x)Lax(L4)Cl3·y4H2O (x was the mole fraction of La(III) in the mixed ions, the value was 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, respectively; y1, y2, y3, y4 were plus integer) were studied, and the mechanism of fluorescence enhancement effect was discussed detailedly.     

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.     

Influence of La and Nd Complexes with Citric Acid on Cellulase Activity and Its Mechanism

Influence of La and Nd Complexes with Citric Acid on Cellulase Activity and Its Mechanism