Interaction of TbCl3 and lanthanide complexes with poly（N-vinylpyrrolidone）

The interaction of TbCl3 and lanthanide(III) β-diketonate complexes with poly(N-vinylpyrrolidone)(PVP) polymer was studied using fluorescence spectroscopy. In the presence of PVP the emission of Tb3+ in ethanolic solution of TbCl3 significantly increased owing to the excitation energy transfer from PVP to Tb3+ ions, which was more efficient as compared to a direct excitation of the Tb3+ 4f75d1 levels. In contrast, emission of NEt4Tb(hfa)4 and NEt4Eu(hfa)4 complexes was almost completely quenched in solution containing PVP. The PVP bound both Ln3+ ions and hfa ligands which caused decomposition of Ln-hfa complexes and switched off the excitation energy transfer from the ligand to the emitting Ln3+ ion. The important role of hydrogen bonds in stabilization of interaction of hfa ligands with PVP was indicated.     

Synthesis, Characterization and Antitumor Activity of Lanthanum （Ⅲ） Complex with Demethylcantharidate

Becausetherareearthelementshashigheraffini tytotumortissuethantonormaltissue,theradioac tiverareearthelementswereusedtodiagnoseand treatthemalignanttumorsintheearlieryears.Howev erthetherapeuticeffectwiththoseelementsisnot good.Recently,moreresearchesfocu…     

Synthesis,spectral characterization,thermal and biological studies of lanthanide（III） complexes of oxyphenbutazone

Lanthanide（III） complexes of 4-butyl-1-（4-hydroxyphenyl）-2-phenyl-3,5-pyrazolidinedione （OPB） were prepared by ho-mogeneous precipitation. The solid complexes were characterized by elemental analysis, magnetic susceptibility data, molar conduc-tivity measurements and IR, UV-Vis, mass, 1H NMR and 13C NMR spectral methods. The thermal decomposition of the complexes under static air atmosphere was investigated by simultaneous TG/DTG at a heating rate of 10 °C/min. The final decomposition prod-ucts were found to be metal oxides. The spectroscopic data suggested that OPB acted as a bidentate, mono-ionic ligand coordinating through two carbonyl oxygens of the pyrazolidinedione ring. The kinetic and thermodynamic parameters such as activation energy, pre-exponential factor and entropy of activation for each step of the decomposition reactions were evaluated using Coats-Redfern and MacCallum-Tanner equations. The negative entropy values of the complexes indicated that the activated complexes had a more or-dered structure than the reactant and that the reactions were slower than normal. Investigations of antimicrobial activity of the com-pounds were carried out by the disk diffusion technique.     

Studies on synthesis and fluorescent property of rare earth complexes RE（ABMF）2AA and copolymers RE（ABMF）2AA-co-MMA

Four new complexes RE(ABMF)2AA (RE=Sm, Eu, Tb, Dy) were synthesized by the reaction of RECl3·6H2O with acrylic acid (HAA) and 1-(2-furyl)-3-phenyl-1,3-propanedione (ABMF). The copolymerization of the rare earth complexes with methyl methacrylate was studied by using 2,2-azobis-isobutyronitrile as an initiator. The composition and structure of the four complexes were characterized by elemental analysis, UV-vis and FTIR. The glass transition temperature and molecular weight of the copolymers were determined. Photoluminescent measurement showed that ligand ABMF could efficiently transfer the energy to Sm3+ and Eu3+ ions in the complexes and sensitize the luminescence of the rare earth ions, but could not sensitize Tb3+ and Dy3+ ions. As a result, both Sm3+ and Eu3+ complexes emitted the characteristic fluorescence of Sm3+ and Eu3+ ions due to the f-f transitions. The four copolymers could emit strong fluorescence of the rare earth ions.     

Study on Interaction Energy of PAMAM/Lanthanide（ Ⅲ ） by Molecular Dynamics Method

PAMAM/lanthanide （Ⅲ） nanocomposite was studied by molecular simulation method. Molecular simulation enabled study of the lanthanide tetrad effect at atomic level. However, PAMAM dendrimer exhibiting unique properties such as nanometer size and highly functionalized terminal surface provided a novel space for lanthanide （Ⅲ） to show their peculiar tetrad effect. The results showed that total energies of PAMAM/lanthanide（Ⅲ） nanocomposites presented obvious tetrad effect and special double-double effect. Nd, Gd, and Er fell to the lower point and Gd fell to the lowest point in the TE-Ln curve with four groups. In order to explain the tetrad effect, kinetic energy （KE） and potential energy （PE） were analyzed. The KE curve consisted of three W-type parts （La - Pm, Pm - Tb, Tb - Tm, and the latter two W-type part were axial symmetry） and an exception part （Yb - Lu）. It also showed that the KE of odd atomic number was higher than the even one＇s with exception of Yb and Lu. Furthermore, decomposed potential energies gave out the atomic-level subtle difference of lanthanide which present more regulations for Eu（Ⅲ） - Lu（Ⅲ） compared with La（Ⅲ） - Sm（Ⅲ）. And also Ho-valley and three platforms （Sm - Eu, Td - Dy, Er - Tm） were discovered that refect the regular change of nanocomposite structures. Additionally, there are distinct correlations between Ebond and EInversion, EAngle and EVDW, Eworsion and ECoul, respectively. Therefore, PAMAM could be used in separation of lanthanide by changing conditions.     

Characterization,crystal structure and luminescence properties of a new europium（Ⅲ） complex with macrocyclic ligand derived from 2,6-diformyl-4-methylphenol and diethylenetriamine

The title compound （13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.1^11,15]-triaconta-1 （29）,2,9,11,13,15（30）, 16,23,25,27- decaene-29,30-diol-N^3, N^6, N^9, O^29, O^30）-bis （nitrato-O,O＇）-europium （Ⅲ） nitrate hydrate （[EuL（NO3）2]（NO3）·H2O, L denotes the macrocyclic ligand） was prepared and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structure was determined by X-ray diffraction. The crystal crystallized in the monoclinic system, space group C2/c with a=2.3757 （4） nm, b=1.4302（3） nm, c=1.9584（3） nm, β=91.654（5）°, M=818.60, V=6.651（2） nm^3, Z=8, D=1.635 g/cm, F（000）=3312, R=0.0542, wR=0.1045. The central ion Eu^3＋ was nine-coordinated in the coordinaton geometry of a distorted tricapped trigonal prism. The macrocycle was coordinated through two oxygen and three nitrogen atoms. Two nitrate are chelate in the opposite positions of the macrocycle, the third nitrate being ionic. At room temperature, excitation of the title complex gave rise to the characteristic emissions of the Eu^3＋ ion.     

Synthesis and Characterization of Some Lanthanide（Ⅲ） Complexes with 4- [N-（2-methoxy benzylinine）formy1]-2, 3-dimethyl-1-phenyl-3-pyazolin-5-one

A series of seven novel lanthanide（Ⅲ ） nitrato complexes with 4-[ N-（2-methoxybenzylimine）formyl] 1-2, 3- dimethyl-1-phenyl-3-pyazolin-5-one （2mbfa）, were synthesized. These complexes were characterized by elemental analysis, molecular mass determination, conductance and magnetic moment measurements, IR, UV-visible, and ^13CNMR spectral studies, In these complexes, the Schiff base, 2mbfa, acts as neutral bidentate ligand by utilizing the carbonyl oxygen and azomethine nitrogen as donor sites. All the three nitrate ions are also coordinated unidentately with 7 coordination for the lanthanide（Ⅲ） ions with a tentative monocapped octahedral geometry for the complexes. All the seven lanthanide（Ⅲ） complexes have a general formula, [ Ln（2mbfa）：（NO3）3 ].     

Adsorption of Er（ Ⅲ ） and Its Mechanism on Diglycolamidic Acid Resin

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Microwave assisted synthesis,spectroscopic, thermal,and antifungal studies of some lanthanide（Ⅲ） complexes with a heterocyclic bishydrazone

A bishydrazone formed by the condensation of isatinmonohydrazone and salicylaldehyde reacted with lanthanide（Ⅲ） chloride to form complexes of the type [Ln（HISA）2Cl3], where, Ln=La（Ⅲ）, Ce（Ⅲ）, Pr（Ⅲ）, Nd（Ⅲ）, Sm（Ⅲ）, Eu（Ⅲ）, or Gd（Ⅲ） and HISA= [（2-hydroxybenzaldehyde）-3-isatin]bishydrazone. Both reactions were carried out under microwave conditions. The ligand and the metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV visible, infrared, far infrared, and proton NMR spectral data. The ligand acted as neutral tridentate, coordinating through the carbonyl oxygen, azomethine nitrogen, and phenolic oxygen without deprotonation. The ligand and lanthanum（Ⅲ） complex were subjected to X-ray diffraction studies. The X-ray diffraction pattern of ligand exhibited its crystalline nature and that of the lanthanum（Ⅲ） complex indicated its amorphous character. The thermal decomposition behaviour of the complex, [La（HISA）2Cl3], was examined in the temperature range of 40-800 ℃ using TG, DTG, and DTA. The ligand and the metal complexes were screened for their antifungal activities.     

Eu（Ⅲ） complexes involving 1,3,5-triazine diphosphine oxides

The 1,3,5-triazine diphosphine oxide ligands with donor-acceptor properties formed strong complexes with europium(III) ion in acetonitrile. Spectrophotometric titrations and mass spectra indicated that two ligands coordinated to one europium ion. The stability constants varied from 11.64 to 14.60 (log β). Binary complexes exhibited rather weak luminescence in solution. 1,3,5-triazine diphosphine oxides engaged as co-ligands in Eu(III) (2-thenoyltrifluoroacetonate)₃ complex contributed to the overall photoluminescence and allowed for excitation with longer wavelengths than the parent complex.     

Synthesis, spectroscopic characterization and thermal studies of some lanthanide(Ⅲ) nitrate complexes with a hydrazo derivative of 4-aminoantipyrine

A heterocyclic ligand synthesized by the coupling of diazotized 4-aminoantipyrine with acetylacetone reacted with lanthanide(III) nitrate to form complexes of the type [Ln(HAAP)₂(NO₃)₃] where, Ln=La(III), Ce(III), Pr(III), Nd(III), Sm(III), or Gd(III) and HAAP= 3-{[2-(N-1-phenyl-2,3-dimethylpyrazol-3-in-5-on-4-yl)]hydrazone}pent-2,3,4-trione. The ligand and metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV-Visible, infrared, far infrared and proton NMR spectral data. The spectral data revealed that the ligand existed in the hydrazo form and coordinated to the metal ion without deprotonation in a neutral tridentate manner, through carbonyl oxygen of pyrazolone ring, hydrazo nitrogen and carbonyl oxygen of the acetylacetone moiety. The molar conductance values adequately supported their non-electrolytic nature. The ligand and the praseodymium(III) complex were subjected to X-ray diffraction studies. Thermal decomposition behavior of the lanthanum(III) complex was also examined.     

Microwave assisted synthesis, spectroscopy and biochemical aspects of lanthanum(Ⅲ) and praseodymium(Ⅲ) complexes with oxadiazole functionalised dithiocarbazinates

The new lanthanum (Ⅲ) and praseodymium (Ⅲ) complexes of the general formula [Ln(L)3] (Ln=La(Ⅲ) or Pr(Ⅲ); LK=potassium salt of dithiocarbazinates) were prepared by both, conventional thermal and by the use of microwave technology. Elemental analyses, elec-trical conductance, magnetic moment and electronic, infrared, far-infrared, 1H and 13C NMR spectral studies were used to characterize the complexes. The molecular weights of few complexes were determined by FAB-mass spectra. Nephelauxetic ratio, covalency parameter and bonding parameter for these complexes were also calculated. The probable structures of the complexes were proposed. The antifungal and antibacterial activities of the complexes were evaluated. The activities were correlated with the structures of the compounds.     

Progresses in electroluminescence based on europium（III） complexes

The research on electroluminescence based on europium(III) complexes has come to an important phase. This article reviewed the progresses in photoluminescence and electroluminescence of Eu(III) complexes in recent years from the views of the design of Eu(III) complexes and optimization of device structures, and discussed some important factors influencing electroluminescence performance. The problems existing in the practical application such as the volatility and thermal stability of Eu(III) complexes in this area were discussed, and the possible corresponding solutions were briefly prospected.     

Synthesis, structures,thermal and magnetic properties of a series of lanthanide [Ln=Sm, Gd, Er, Yb] complexes with 4-quinolineacarboxylate

A series of lanthanide binuclear complexes, [Ln2(L)6(H2O)4]·2H2O (Ln=Sm(III), Gd(III), Er(III), Yb(III), HL=4-quinolineacarboxylic acid, were synthesized by reactions of corresponding rare earth salts with 4-quinolineacarboxylic acid at room temperature and were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. X-ray diffraction analyses showed that they exhibited the same binuclear architecture and crystallized in monoclinic system and P21/c space group. In four complexes, each metal center adopted nine-coordinated mode coordinated by nine O atoms from two H2O molecules and three carboxyls of three ligands, and HL showed three different coordination modes. The variable-temperature magnetic susceptibility showed that complex [Gd2(L)6(H2O)4]·2H2O performed very weak antiferromagnetic property at low temperature and exchange was almost paramagnetic at high temperature. Complexes [Er2(L)6(H2O)4]·2H2O and [Yb2(L)6(H2O)4]·2H2O performed dominating antiferromagnetic coupling.     

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)Cl(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) nm3, Z=4, Dc=1.416 mg/m3, 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) nm3, Z=4, Dc=1.407 mg/m3, μ=1.728 mm-1, F(000)=1580, R=0.0670, wR=0.1385.     

Pr（Ⅲ） and Nd（Ⅲ） Absorption Spectroscopic Probe to Investigate Interaction with Lysozyme （HEW）

Pr（ Ⅲ ） and Nd（ Ⅲ ） can be utilized as absorption spectroscopic probes to investigate the interaction of biomolecules like Lysozyme （HEW） with Ca（ Ⅱ ） in-vitro ; the most abundant metal ion in the human body system. The spectroscopic techniques involving comparative absorption, absorption difference, and quantitative intensity analysis using 4f-4f transitions are utilized for changes in the inner sphere coordination pattern of Pr（ Ⅲ ） and Nd（Ⅲ ） in solution as well as in solid state. The present study deals with an important biomolecule in human metabolism, that is, Lysozyme （HEW）. The absorption er-Condon the probab spectral parameters such as the oscillator strength （P）, the Judd-Ofelt （Tλ） intensity parameters, and the Slatinter electronic parameters are calculated using chi square methods. The obtained results are used to determine le geometry of the complex in the solution, the nature of the bond between Pr（Ⅲ）/Nd（Ⅲ） with lysozyme, and the inner sphere coordination environment of f-f transitions. The results obtained from various experimental conditions are utilized to investigate the coordination changes in the Pr（Ⅲ）/Nd（Ⅲ） complexes caused by different coordinating sites of lysozyme, normalized bite, denticity, the solvent nature, the coordination number, the nature of bond and other parameters to mimic the interaction of the Ca（ Ⅱ ） ion with such biomolecule.