Preparation of Ternary Lanthanide Complexes with Unsaturated Acid and 1,10-Phenanthroline, and Their Anti-Inflammatory Action

Four ternary lanthanide complexes with unsaturated acid and 1,10-phenanthroline are prepared in methanol and characterized by elemental analysis, molar conductance, UV, IR, (()~1H) NMR and XPS. The results from this paper show that the complexes Ln(phen)(SA)_3·2H_2O or Ln(phen)(CA)_3·H_2O (Ln=Ce(Ⅲ), Sm(Ⅲ) and Eu(Ⅲ), (phen=1,10-)phenanthroline, SA=Sorbate and CA=Cinnamate) has better anti-inflammatory effect than cerium nitrate and their gremores are steadier than cerium nitrate gremor. And there is a kind of medicament which can replace the cerium nitrate gremor completely in treating burn.

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

The two compounds of [Ln（2-FBA）3·2,2＇-bpy ]2（2-FBA = 2-fluorobenzoato, 2,2＇-bpy = 2,2＇-bipyridine, Ln = Eu（1 ）, Dy（2）） were synthesized and their structures were determined by X-ray diffraction method. Crystallized complexes 1 and 2 are isomorphous, monoelinie system with P21/n space group. The two complexes are binuclear molecule with an inversion center. The two lanthanide ions are linked by four bridged 2-FBA ligands and each lanthanide ion is further bonded to one chelated bidentate 2-FBA ligand and one 2,2＇-bipyridine molecule. The coordination number of metal ion is eight. The europium complex exhibits strong red fluorescence. ^5D0→^7Fj（j = 1 - 4） transition emission of Eu^3＋ ion was observed.

Synthesis, Characterization and Antioxidative Activity of Lanthanide Complexes with Genistein

Six genistein lanthanide complexes, LnL_2 (OAc)·nH_2O [Ln=La(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), (Tb(Ⅲ),) Dy(Ⅲ); L=genistein; n=4, 7, 8] were synthesized and characterized on the basis of elemental analyses, IR, (()~1H) NMR spectra and molar conductivity. The scavenging activity of genistein and five lanthanides complexes on the hydroxyl free radicals (OH·) was also investigated by spectrophotometric methods. The results show that the scavenging activity of the complexes is better than that of the ligand and their scavenging ability can be assembled in the following order: Sm>La>Dy>Eu>Tb>L.

Synthesis and characterization of lanthanide complexes containing a bulky tridentate [N,N,O] Schiff base ligand

The lanthanide complexes containing a bulky tridentate [N,N,O] Schiff base ligand 3,5-But2-2-（OH）C6H2CH=N-8-C9H6N （HL） were synthesized and characterized. The reaction of anhydrous LnCl3 with NaL formed in situ in a 1：1 molar ratio in THF at room temperature afforded the lanthanide Schiff base dichloride complexes LnLCl2（DME） （Ln=Eu （1）; Sm （2））. Complexes 1 and 2 can be used as precursors for the synthesis of the lanthanide cyclopentadienyl Schiff base derivatives. The reactions of complexes 1 and 2 with one equiv of NaCH3C5H4 in THF provided the desired products LnL（CH3C5H4）CI（THF）.THF （Ln=Eu （3）; Sm （4）） in good isolated yields. These complexes were characterized by elemental analysis, IR spectra, and X-ray structural determination, in the case of complexes 3 and 4. The crystal data of complex 3 are monoclinic, P21/C space group, a=1.3370（2） nm, b=1.5190（2） nm, c=1.8910（3） nm, β=109.846（4）°, V=3.6125（8） nm^3, Z=4, Dc=1.416 mg/m^3,μ=1.847 mm^-1, F（000）=1584, R=0.0707, wR=0.1350. The crystal data of complex 4 are monoclinic, P21/c space group, a=1.3383（1） nm, b=1.5210（2） nm, c=1.8960（2） nm, β =109.878（3）°, V=3.6293（7） nm^3, Z=4, Dc=1.407 mg/m^3, μ=1.728 mm^-1, F（000）= 1580, R=0.0670, wR=0.1385.

Highly Luminescent Host-Guest Systems Based on Zeolite L and Lanthanide Complexes

Supramolecular incorporation of lanthanide complex has been obtained by loading of organic ligand into Eu3+-exchanged zeolite L. This was achieved by a two-step procedure: (1) zeolite L was ion-exchanged with Eu(Ⅲ) ions; (2) organic ligand was then loaded into the channels of the Eu3+-exchanged zeolite by gas diffusion procedure. Loading of ligand into the channels of zeolite L was confirmed by element analysis. Luminescence spectroscopy has confirmed that lanthanide complex are formed in the nanochannels of zeolite L crystals. In addition to the sharp emissions of lanthanide ions, broad band ranged from 350～500 nm can also be observed. This study provides alternative method for fabricating full-color display materials.

Synthesis, Characterization, and Reactivity of Amine Bis(phenolato) Cyclopentadienyl Lanthanide Complexes

（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.

Lanthanide Complex [Nd(dpdo)_4(H_2O)_3][ClO_4]_3·4.5H_2O·dpdo Containing Framework Based on 4,4′-Dipyradine-Dioxide

A novel lanthanide coordination polymer formulated as [Nd(dpdo) 4(H 2O) 3] 3·4.5H 2O·dpdo 1(dpdo=4,4′-dipyrazine-dioxide) was synthesized and structurally characterized. The Nd 3+ ions are bridged by dpdo ligands in a cis-mode to form a zigzag chain along direction. Meanwhile, each Nd 3+ ion is coordinated with three terminal dpdo molecules. One of them is overlapped with the bridging one through π-π stackings, and the other two are bound to the opposite directions of the bridging ones, producing a ribbon-like motif with rectangular cavity. These adjacent ribbons are connected through inter-molecular π-π stackings to give parquet-like architecture with a large rectangular channel (1.108 nm×1.660 nm) in which the crystal lattice water molecules and ClO 4 - anions are included. Thermal analysis shows that the solvate dpdo and water molecules can be removed at lower temperature, while coordinated dpdo molecules are lost simultaneously at higher temperature.

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

A series of novel rare earths complexes with Schiff base of pridoxylidence-glycine acid (HL) were synthesized in absolute methanol under argon atmosphere. The complexes were characterized by elemental analysis, molar conductivity, IR, UV spectra, and H-NMR spectra et al. Data indicate that the complexes have a general formula Ln LCl2.3H(2)O (Ln = La, Y, Sm, Gd, Dy, Yb; L = C10H11N2O4). Effects of the complexes (Ln = La) on physiological and biochemical indexes of plants under Pb stress were studied. The experiments shown that the complexes obviously mitigated Pb pollution results in decreasing of chlorophyll content, rising of cell membrane permeability, changing catalase(CAT) and distribution of Pb.

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

By the reaction of Cp 3Ln with HL(Cp=η 5 C 5H 5, cyclopentadienyl; Ln=Yb, Tm, Er, Ho, Dy, Gd, Pr; HL=benzohydroximic acid), seven new complexes of the general formula Cp 2LnL were synthesized. All the complexes were characterized by elemental analysis, infrared spectra, and mass spectra. Based on these data, the probable structure was proposed.

POLYMER-SUPPORTED LANTHANIDE COMPLEXES FOR THE POLYMERIZATION OF BUTADIENE

The characteristics of styrene-acrylic acid copolymer supported lanthanide complexes (SAAC Ln) (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tin, Yb, and Lu) were described. A comparison of the activities of SAAC·Ln was made. It was found that in the polymerization of butadiene, a peak in activity appeared at Nd and Pr, Sin, Eu and the heavy lanthanides exhibited low or no activities. The effects of some factors on the activities were discussed. The microstructure of the polymers obtained with all the lanthanides in the series were the same and the content of cis-1, 4 polybutadiene attained was more than 98%.

SYNTHESES AND SPECTROSCOPIC PROPERTIES OF LANTHANIDE COMPLEXES, Ln(acac)_3(Ph_3PO)_3

A series of new complexes of formula Ln(acac)_s(Ph_3PO)_3 (where Ln^(3+)=Nd^(3+), Sm^(3+), Eu^(3+), Tb^(3+), Ho^(3+)) have been prepared and characterized. The coordination of two ligands with lanthanide ions are studied by IR spectra, ~1H, ^(13)C, ^(31)P-NMR and metal-ligand charge tranafer tranaition is also discussed via electronic adaorption and luminescence spectroscopy.

LANTHANIDE COMPLEXES OF ACETYLACETONATE-MESO-TETRA-(4-PYRIDYL)PORPHYRIN

New tanthanide comptexes of acetylacetonate-meso-tetra- (4-pyridyt)porphyrin(LnTpypacac,Ln=Dy,Ho,Yb,Lu,H_2Tpyp= tetra-(4-pyridyl)-porphyrin,Hacac=acetylacetone)were prepared by reaction of Ln(acac)_3·3H_2O with H_2Tpyp and were characterized by elemental analyses,ultra-viotet spectra,infrared spectra and thermal analyses.

The Double-Double Effect of Lanthanide Complexes with Styrene-Acrylic Acid Copolymer

The double-double (or tetrad) effect of low molecular lanthanide complexes has been reportedsince the effect was discovered by Fidelis and Siekierski.However,so far no description concerning thedouble-double effect of macromolecular lanthanide complexes has been published in literature.We have been successful in preparing lanthanide complexes with styrene-acrylic acid copolymer,someof which exhibite high activitiest in butadiene polymerization.It was found that the complexes showedthe double-double effect as they were characterized.In the present paper,the SAAC·Ln IR spectra whichcharacterize the double-double effect have been discussed in detail.

CRYSTAL STRUCTURE OF A HETERONUCLEAR LANTHANIDE COMPLEX OF ERBIUM-YTTRIUM AND GLYCINE[ErY(GlY)_6(H_2O)_4](ClO_4)_65H_2O

The title complex [ErY(Gly)_6(H_2O)_4](ClO_4)_6 5H_2O has been synthesized.Its crystal structure has been determined by X-ray diffraction method.The crystal is triclinic with space group P1.The unit cell parameters are as follows:a=11.518(4),b=14.105(7),c=15.530(6) ,α=96.61(3), β=102.74(3),γ=105.70(3)°,V=2327.7(17) ~3,Z=2,Dc=2.091g/cm^3.The structure has been refined to a final R of 0.0785.The crystal is an infinite chain complex,in which four carboxyl groups from glycine molecules bridge the Er(Ⅲ)and Y(Ⅲ)ion,other two carboxyl groups bridge two adjacent Er(Ⅲ)or two Y(Ⅲ)ions.

Crystal Structures and Photoluminescence Properties of Two Lanthanide Complexes Constructed by Flexible 1,2-Phenylenediacetic Ligand

Two 3D Ln-organic coordination frameworks（Ln = Pr3＋ for 1 and Er3＋ for 2） have been constructed. Single-crystal X-ray diffraction analysis reveals that the two complexes have similar structures and belong to the monoclinic C2/c space group. The trans-μ4-（η2：η1）-（η1：η1） 1,2-pda2- anions link the LnIII centers to generate a 2D network containing helical motif. The dimensionality is extended into a 3D architecture through cis-bis（μ2-η2：η1） 1,2-pda2- anions linking. The geometry of Ln3＋ ions is single-capped anti-square prism. Two complexes were characterized by IR spectra and thermogravimetric analysis. The solid fluorescence of 1 and 2 was also investigated at room temperature.

Circularly polarized luminescence of lanthanide complexes:From isolated individuals,discrete oligomers,to hierarchical assemblies

Circularly polarized luminescence(CPL)is the emission featured spatial orientation equivalent to circular dichroism.Owning to the unique magnetic dipole-allowed but electric-dipole-forbidden 4f→4f transitions,chiral lanthanide complexes have been recognized as ideal candidates to achieve unprecedented luminescence dissymmetry factor(glum).Their inherent electric-dipole-forbidden transition can be partly allowed,through the rational design of coordination ligands to lower the surrounding symmetry,further endowing them with relatively high quantum yields(QYs).Moreover,the blossom of supramolecular chemistry in lanthanide complexes allows for the construction of discrete oligomers and hierarchical assemblies,rendering them with enhanced chiroptical activities.Here,we deploy this review by summarizing recent advances in the chiroptical properties of lanthanide complexes,spanning multiple scales from isolated mononuclear individuals,discrete polynuclear oligomers,to infinite hierarchical assemblies.We first introduce the basic concept and several important parameters for the assessment of CPL activity.Then,isolated mononuclear lanthanide complexes coordinated with different types of antennas,along with the unique chirality transfer and induction in achiral lanthanide complexes were discussed.Next,the systematical discussion on chiroptical properties in discrete polynuclear lanthanide oligomers and infinite hierarchical lanthanide assemblies was presented.Meanwhile,the state-of-the-art applications of CPL-active lanthanide complexes were revisited.We end up this review with the conclusion and prospects,involving the rational design of ligands,directed and hierarchically precise self-assembly,and extending applications of chiral lanthanide complexes.

Advances in luminescent lanthanide complexes and applications

Luminescent lanthanide complexes have been widely investigated as light emitting materials in bio-imaging and sensing, solid state lighting and display, anti-fake tags and light conversion films, due to their characterized photophysical properties including large Stokes shift, long lifetime, and sharp emission spectrum, arising from the sensitized f-f transitions. In this review, we summarize the most recent advances in luminescent lanthanide complexes and their applications from 2015 to August 2017 concerning of general concepts to potential applications. We first introduce the basic concept of sensitized luminescence of lanthanide complexes and the strategies used for highly luminescent complexes. Then recent varieties of luminescent lanthanide complexes and their hybrid materials are presented. Finally, applications are discussed in detail.

Synthesis and spectral characterization of lanthanide complexes with 1,2-diphenyl-4-butyl-3,5-pyrazolidinedione: Luminescent property of Tb(Ⅲ) complex

The complexes of rare earth elements with 1,2-diphenyl-4-butyl-3,5-Pyrazolidinedione （PBH, phenylbutazone） were synthesized and characterized by elemental analysis, molar conductance, IR, UV-Vis, EPR and magnetic moment measurements. Based on these studies the complexes were formulated as [Ln（PB）3（H2O）2].nH2O, where Ln=Eu（III）, Gd（III）, Tb（III）, Dy（III） and Er（III）. From IR spectra, it was found that PBH acted as a bidentate mono-ionic ligand coordinating through two carbonyl oxygen of the pyrazolidinedione ring. The thermal analysis of all the complexes was carried out at a heating rate of 10 oC/min. The kinetic aspects of the complexes were evaluated. The nega-tive entropy value of the complexes indicated a more ordered state for the activated complexes. The photoluminescence property of Tb（III） complex was investigated. It showed all the characteristic emission peaks of Tb^3＋ with a life time of 0.98914 ms.

Structure regulation for ultra-high luminescence quantum yield lanthanide complex and simultaneous detection of cancer marker and ferrous ion

The exploitation of a highly selective and sensitive probe to detect both cancer marker and metal ion is of great importance.In this work,the "one stone two bird" agent of 1,10-phenanthroline(phen) is designed to disrupt the polymeric lanthanide MOFs(LnMOFs,[Ln(CHO_(2))_(3)]n,Ln=Tb,la;Eu,1 b,CHO_(2)=formic acid) {[Ln(CHO_(2))_(4)·(C_(2) H_(8) N)]n,Ln=Y,2 a;Gd,2 b;Dy,2 c,C_(2)H_(8) N=dimethylamine}) into a soluble mononuclear species [Ln(phen)_(2)(NO_(3))_(3),Ln=Tb,3 a;Eu,3 b] as well as to provide an antenna for efficient photons absorption,resulting in an ultra-high luminescence quantum yield(QY,90%) europium complex.The luminescence QY is among the highest record of monomeric(zero-dimensional) lanthanide complexes.Furthermore,mononuclear Tb3+complex(3 a) functions as a multiplex sensor towards both Fe^(2+)and cancer marker of 5-hydroxyindole-3-acetic acid(5-HIAA).Importantly,the limit of detection(LOD)for sensing 5-HIAA is an ultra-sensitive value of 1 × 10 s mol/L,which is even lower than that necessary for the early diagnosis of carcinoid tumors.More interestingly,sensing results in simulated urine reveals that 3 a has potential application for early diagnosis in the clinic.