STUDIES ON COMPLEXES OF RARE EARTHS WITH CROWN ETHERS(V)-SYNTHESIS AND CHARACTERIZATION OF THE COMPLEXES OF RARE EARTH NITRATES WITH 2,2'-DINITRO-4,5,4',5'-BIS-(15-CROWN-5)-DIBENZO DISULFIDE

Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6H_2O(RE=Ce, Pr, Nd) have been synthesized in acetonitrile. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X-ray powder diffraction analysis, molar conductance and measurements of solubility in some general solvents.

STUDIES ON COMPLEXES OF RARE EARTHS WITH CROWN ETHERS(Ⅳ)SYNTHESIS AND CHARACTERIZATION OF THE COMPLEXES OF RARE EARTH NITRATES WITH 4'-BROMO-5'-NITROBENZO-15-CROWN-5

Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.

STUDIES ON RARE EARTH COMPLEXES WITH CROWN ETHERS ⅩⅧ——Synthesis,Characterization and Crystal Structure of[Sc(NO_3)_3(H_2O)_2]·(15-Crown-5)

The single crystal of the complex [Sc(NO_3)_3(H_2O)_2]·(15C5) has been prepared in acetonitrile.The new complex has been characterized by elemental analysis,IR spectra,solubility and molar conductance measurements.The structure of the complex is determined by single crystal X-ray diffraction analysis.

ELECTRONIC STRUCTURE AND BOND CHARACTER OF COMPLEXES OF RARE EARTH CHLORIDES WITH CROWN ETHERS

A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.

Synthesis, Characterization and Fluorescence of Rare earth Nitrate Complexes with Triaza-crown Ether Derivative

Four new complexes of rare earths with a triaza crown ether (L) derived from N 3O 2 macro cycle 1,12,15 triaza 3, 4: 9,10 dibenzo 5, 8 dioxacycloheptadecane were synthesized and characterized by elemental analysis, IR, molar conductance, TG DTA analysis and fluorescence spectra. The composition of the complexes determined as [RE(NO 3) 3L·3H 2O]·H 2O (RE=Sm, Eu, Tb and Dy). It is found that Sm 3+ , Eu 3+ , Tb 3+ and Dy 3+ complexes all show strong fluorescence emission in the solid state. Among these complexes, Tb 3+ complex has the strongest luminescence intensity. It shows that the ligand L triplet state energy matches 5D 4 energy level of Tb 3+ . In the Eu 3+ complex, η ( 5D 0→ 7F 2/ 5D 0→ 7F 1) is 2.6, which indicates that Eu 3+ locates at the asymmetric coordination field.

Ternary Complexes of Rare Earth Nitrate with B-15-C-5 and 4-Picoline N-Oxide

A series of ternary complexes of rare earth(Ⅲ)nitrate with benzo-15-crown-5 and 4-picoline N-oxide have been prepared.They have the general formula of RE(NO_3)_3·2(4-picNO)·3H_2O·(1/2)(B-15-C-5) (RE=La～Tm).Their physico-chemical properties have also been studied with conductance,thermal analysis and IR absorption spectroscopy.

Novel Approach to Characterization of Rare Earth Complexation with 1, 5-Bis(2-Hydroxy-5-Chlorphenyl)-3-Cyanoformazan in Presence of Cetyltrimethylammonium Bromide

The ternary interaction of 1, 5 bis(2 hydroxy 5 chlorphenyl) 3 cyanoformazan (HCPCF) with cetyltrimethylammonium bromide (CTAB) and rare earths (RE: Yb, Dy, Er and Eu) was investigated at pH 9.84 by the microsurface adsorption spectral correction technique (MSASC). The aggregation of HCPCF on CTAB obeys the Langmuir isothermal adsorption and the interaction of RE with the HCPCF CTAB aggregate was first found to accord with the monolayer binding. The effects of temperature and ionic strength of solution on the aggregations were made. The binary aggregate and the ternary complex were characterized.

Dioxygen Affinities and Biomimetic Catalytic Oxidation Performance of Transition-metal Complexes with Unsymmetrical Bis-Schiff Bases

The oxygenation constants and thermodynamic parameter (ΔHo, ΔSo) of Co (II) complexes with unsymmetrical bis-Schiff baeses were measured and their Mn(III) complexes as models of mimicking monooxygenase were employed to catalyze epoxidation of styrene. The effect of substituent R in a salicylidene of ML1~ML4 [ M = Co (II), Mn (III)Cl ] on the dioxygen affinities and biomimetic catalytic oxidation performance were also investigated. Among them, the MnL4Cl containing a pendant benzoaza crown ether ring showed highest conversion and selectiviy up to 54.9% and 96.9% respectively.

Synthesis and Thermal Behaviour of Lanthanide Complexes of 4′[（Cholesteryloxy）Carbonyl]—Benzo—15—Crown—5

Lanthanide complexes of a steroid-substituted benzocrown ether were synthesised. The metal-to-ligand ratio of all the metal complexes is 1∶1. The ligand 4′-[(cholesteryloxy)carbonyl]-benzo-15-crown-5 is a monotropic liquid crystal, displaying a cholesteric mesophase. The lanthanide complexes with nitrate counter-ions form a highly viscous mesophase, decomposing at the clearing point. The transition temperatures change as a function of the lanthanide ion. The corresponding lanthanide complexes with dodecylsulphate (DOS) counter-ions do not form a mesophase. In both cases, the metal complexes have a much lower melting point than the parent ligand.

Synthesisand Crystal Structure of the 2:2 Complexes Between Lighter Rare Earth Nitrates and N,N,N',N'-Tetraphenyl-3,6-Dioxaoctanedioicdiamide

The 2:2 complexes between lighter rare earth nitrates and N,N,N',N'-tetraphenyl-3,6- dioxaoctanedioicdiamide(TDD),[RE(TDD)_2(H_2O)_2][RE(NO_3)_6]1—4(1,2,3,4 for RE=La,Ce,Pr, Nd,respectively)and[Ce(TDD)_2(H_2O)_2][Ce(NO_3)_6]·CH_3OH·2H_2O_5,have been synthesized and characterized.The crystal structure of 5 reveals that TDD acts as a tetradentate forming a half-ring coordi- nation structure.There is a little difference in the conformations of the two TDDs.The Ce ions are 10-and 12-coordinated for the complex cation and anion,respectively,and the coordination polyhedrons are a bi- capped distorted square antiprism and a distorted icosahedron,respectively.

Synthesis and Spectral Properties of Mixed-Ligand Complexes of Lanthanide Perchlorate with Bis-(phenylsulfinyl)ethane and Organic Lewis Bases

Six lanthanide complexes with bis(phenylsulfinyl)ethane(bphse) and organic bases(phen: 1,10 phenanthroline and bipy: 2,2'-bipyridine) were synthesized and characterized by elemental analysis, conductance and spectral (IR, UV Visible) data. The complexes were Ln(bphse) 2(bipy)(ClO 4) 3· n H 2O and Ln 2(bphse) 3(phen) 2(ClO 4) 6·H 2O(where Ln=Nd, Eu and Gd; n =0～2). IR spectral data confirmed that the lanthanide ions were coordinated by oxygen atoms from bphse and nitrogen atoms from phen or bipy. Exitation and emission spectra of Eu complexes were measured and discussed.

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.

Crystal structures of the complexes of rare earth picrates with N, N, N', N'-tetraphenyl-3, 6-dioxaoctanediamide

The complexes of rare earth picrate with N,N,N’,N’-tetraphenyl-3,6-dioxaoctanediamide(TDD),Eu(picc(TDD)] 2CH3CN and [ Y(pic)3(TDD)],have been synthesized.The crystal structures reveal that TDD at is as n tetradentate ligand,forming a ring-like coordination structure with its oxygen atoms together with one oxygen atom of the bidentate pterate In the Eu(Ⅲ) complex,the europium ion with a larger ionic radius lies out of the ring,while in the Y(Ⅲ) complex,the yttrium ion with a smaller ionic radius enters the cavity of the ligand.The structures of the complexes are greatly affected by the ionic radii due to participation of the picrates in coordination.

XPS STUDY ON RARE THEIR COMPLEXES EARTH CHLORIDES AND WITH CROWN ETHERS

I.INTRODUCTION In a previous paper, we reported the molecular configuration and electronic structure of LaCl315-crown-5 complex, and made a theoretical analysis for its chem-

p-Nitrophenyl Picolinate Cleavage by Unsymmetrical Bis-Schiff Base Manganese（Ⅲ） and Cobalt（Ⅱ） Complexes with Aza-Crown Ether or Morpholino Pendants

The unsymmetrical bis-Schiff base manganese（III） and cobalt（II） complexes with either benzo-10-aza-crown ether pendants （MnL1Cl, MnLZCl） or morpholino pendant （MnL3Cl, CoL3） have been employed as models for hy- drolase by studying the kinetics of their hydrolysis reactions with p-nitrophenyl picolinate （PNPP）. A kinetic model of PNPP cleavage catalyzed by these complexes is proposed. The effects of complex structures and reaction temperature on the rate of PNPP hydrolysis have been examined. All four complexes exhibit high catalytic activity and the rate increases with pH under 25℃. The complexes of ligands containing a crown ether group exhibit higher catalytic activities than the non-crown analogues. The catalytic activity of the complexes follows the order Mn（III） 〉 Co（II） under the same ligands.

Synthesis and Fluorescence Properties of Europium, Terbium Doped Zn^(2+), Cd^(2+) and Cr^(3+) Complexes

Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were prepared. By replacing half of the europium or terbium ion with M （M = Zn^2＋, Cd^2＋, and Cr^3＋） using the doped method, and then incorporating it with 18-crown-6 ether and terephthalic acid, six heteronuclear samples EuZnLL＇Cl3·3H2O（1）, EuCdLL2＇Cl3·5H2O（2）, EuCrLL＇Cl4· 4H2O（3）, TbZnLL＇Cl3·4H2O（4）, TbCdLL＇2Cl3·4H2O（5）, and TbCrLL＇2Cl4 ·4H2O（6） （L = terephthalic acid, L＇= 18-Crown-6 ether） were obtained. The elemental analysis, molar conductivities, rare earth complexometry, Fourier Transform Infrared Spectroscopy （FT-IR）, ultraviolet （UV）, TGA, fluorescence intensity, and fluorescence lifetime of the samples were measured. The results showed that there were good luminescence properties for heteronuclear complexes （1）, （2）, （4）, and （5）, which were even stronger than those of the homonuclear complexes Eu2LL＇2Cl4·4H2O and Tb2LL＇2Cl4 ·4H2O, but the luminescence properties of EuCrLL＇Cl4·4H2O, TbCrLL＇Cl4·4H2O were very weak. A possible luminescence mechanism was suggested by the organic-inorganic doped mechanism and the law of intramolecular energy transfer.

Helical ternary complexes of alkaline earth picrates with open-chain crown ether

Four solid complexes of alkaline earth picrates with N,N,N′,N′-tetraphenyl-3,6,9-trioxaundecanediamide (TTD), M (Pic)2TTD (1, M = Mg; 2, M = Ca; 3, M = Sr; 4, M = Ba), have been prepared and characterized by elemental analysis, conductivity measurement, IR spectra, 1H NMR spectra and TG-DTA techniques. Crystal structure of complex 3 shows that the Sr(II) ion is 9-coordinated by five oxygen atoms from TTD and four oxygen atoms from two bidentate picrates, and the coordination polyhedron is distorted tricapped trigonal prism. TTD as a pentadentate ligand forms a right-handed helical coordination structure. The chelating helical chain has a relative fixed radius and then shows a high coordination selectivity to metal ion. The high selectivity of TTD to alkaline earth ions is explained elementarily from the special coordination structures.

VOLTAMMETRIC STUDY ON THE COMPLEXATION OF RARE EARTHS WITH CROWN ETHERS IN ACETONE MEDIA

in our previous paper we reported the complex of Eu3+ with 18-crown-6（18-C-6）giving a reversible voltammetric peak in acetone with Ep=+0.09 V （vs. Ag/AgCl）, which agreed well with that reported by ZHU Tian-pei and YU Feng-lan with E1/20=+0.10 V（vs. SCE）. This reversible peak is not interfered by other rare earths or small amounts of O2 and water. The effects of trace amounts of O2 and water on other rare earths in anhydrous acetone were further investigated. This note presents the

SYNTHESIS AND CHARACTERIZATION OF THE SOLID COMPLEXES OF Eu (Ⅱ,Ⅲ)WITH OCTANEDIOYL-BIS(BENZO-15-c-5)

The study of rare earth complexes with crown ether arouses people’s great interest. The previous research work was focused on the complexes with single crown ether. Because of the coordinated actions with metal ions of the two crown ether cycle activities, the bis (crown ether)has better coordination and selectivity than the single crown ether ligands.

Studies on Coordinations Reaction between Eu（NO_3）_3·3H_2O and Crown Ether 18C6 In Anhydrous Acetonitrile

The solubility of the ternary system Eu(NO2)3·3H2O-18C6-CH3CN at 30℃ has been studied by means of semimicro phase equilibrium. The results indicate that there is only one stoichiometric complex formed in the ternary system. There are two solubility curves for this ternary system. The long one corresponds to the solid phase of the complex Eu(NO3)3·18C6·3H2O and the short one to the solid phase of the 18C6. The curve of refractive indexes for the saturated solutions consists of two branch lines, which correspond to the solubility curves. The behavior of water for this system in equilibrium, has been examined. The mole ratio. H2O/Eu(NO3)3, whether in liquid phase or in solid phase, is always 3: 1. The complex formed in this solvent has been isolated. The composition of this complex has been examined by chemical analysis. The behavior of this complex has also been examined by IR spectra, thermalanalysis and molar conductance.