Structure and Fluorescence Emission of Hetero-Nuclear Complexes of Europium-Lanthanum Nitrates with N, N＇-Substituted Adipamide

A europium-lanthanum hereto-nuclear complex with new ligand N, N‘-dimethyl-N, N‘-diphenyladi-pamide (MPAA) was prepared. The one dimensional chain structure of [ La0.5Eu0.5(MPAA)2(NO3)3] Was determined crystallographicaly. The europium ion and lanthanum ion statistically lie at the position of the metal ion withM= 1/2(La Eu). Each Ln3 ion is nine-coordinated including three bidentate nitrates, three carboxyl groups from three MPAA molecules, in which two MPAA are act as bridge ligand. The intensity of fluorescence of La3 -Eu3 heteronuclear complex A was obviously higher than that of pure Eu3 complex B both in solution and in solid state.     

Synthesis and Structure of a Polymeric Complex [Ce（bphsb）2（NO3）3]n

Polymeric cerium nitrate complex with 1,4-bis (phenylsulfinyl) butane (bphsb) [Ce(bphsb)2(NO3)3]n (1) was synthesized and characterized. The crystal structure of the complex indicated that the ligand bphsb and cerium( Ⅲ ) ion form a polymeric double-bridge chain complex involving 18-membered macrometallocycles. Each cerium ion is coordinated by ten 0 atoms in a distorted 4,4-bicapped square antiprism. In the complex the disulfoxide ligand acts as bis-monodentate O-ligand bridging metal centers.     

Synthesis and Crystal Structure of N-phenylthiocyano-phenylthioformamide-bis （ η5-methylcyclopentadienyl） （tetrahydrofuran） Samarium （Ⅲ）

The insertion reaction of phenyl isothiocyanate into the Ln-S bond was studied. Phenyl isothiocyanate reacted with [(CH3C5H4)2Sm(SPh)(THF)]2 to give the title complex, (CH3C5H4)2Sm[SC(SPh) NPh](THF),in good yield, which was characterized by elemental analyses, IR, ^1H NMR and X-ray structural determination. The crystal structure analysis of complex shows that samarium atom is coordinated by two CH3C5H4 groups, one O atom of THF, and N and S atoms from the SC(SPh)NPh ligand to form a distorted trigonal-bipyramidal geometry.     

Synthesis, Crystal Structure of [ （MeC5H4）2Ln（μ-OCH2 CH2NMe2 ） ]2 （Ln = Sm, Y, Nd） and Their Catalytic Activity for Ring-Opening Polymerization of ε-Caprolactone

Reaction of (MeC5H4)3Ln with HOCH2CH2NMe2 in tetrahydrofuran (THF) gives the new complexes [ (MeC5H4)2Ln(μ-OCH2CH2NMe2)]2(Ln = Sm, Y, Nd) with nitrogen functionalized μ-alkoxide ligand. The complexes were characterized by elemental analysis and IR, and [ (MeC5H4)2Sm(μ-OCH2CH2NMe2)]2 was structurally characterized by the X-ray diffraction to be a dimer formed by two unsymmetric oxygen bridges. The complex has a tricyclic skeleton with the additional two Sm- N bonds via intmmoleeular coordination of OCH2CH2NMe2. The coordination number of the central metal Sm is nine. The tide complexes show good catalytic activity for ring-opening polymerization of ε-capmlactone.     

Synthesis, characterization, fluorescence and DNA-binding studies of europium（Ⅲ） pirates complexes with amide-based 2,3-dihydroxynaphthalene derivatives

Two ligands 2,2′-[2,3-naphthylenebis(oxy)]-bis(N-benzyl(acetamide))(L1) and 2,2′-[2,3-naphthylenebis (oxy)]-bis(N,N-diphenyl (acetamide))(L2) and their europium(Ⅲ) picrate complexes were synthesized. The complexes were characterized by elemental analysis, infra-red (IR), thermogravimetry and differential thermal analysis (TG-DTA) and molar conductivity. Fluorescent experiments showed that the resonance level of the Eu) matched better to the triplet state energy level of the ligand L2 than that of the ligand L1 and the fluorescence in-tensities of the complexes were reduced with the raising coordination ability of solvent. In addition, the interactions between the complexes and DNA were studied by means of spectrometry and cyclic voltammetry. The results suggested that the complexes could bind to DNA through intercalation and the complex 1 binded to DNA more strongly than the complex 2.     

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,     

Self-assembly as a route to one-dimensional lanthanum(Ⅲ) salicylaldimine coordination polymer

The self-assembled formation of a one-dimensional lanthanum salicylald imine coordination polymer was proved by the X-ray diffraction analysis of new l anthanum(Ⅲ) nitrate complex containing N,N’-bis(salicylidene)-1,5-pentanediami ne ligand(H2L) . It was obtained in situ in a one-step,metal-templated condensa tion of salicylaldehyde with 1,5-pentanediamine(cadaverine,biogenic polyamine) and characterized by microanalysis and spectroscopic(IR,ESI-MS,UV-Vis,and 1 H NMR) data. The [La(NO3) 3(μ-H2L) 2]∞ complex displayed 10-coordinate distorted bicapped dodecahedron geometry with unusual coordination pattern of undeprotonat ed salicylaldimines which acted as μ-bridging ditopic ligands using exclusivel y the oxygens as donor atoms with the nitrogen atoms not being involved in the c oordination environment.     

Synthesis,spectroscopic characterization,DNA cleavage and antibacterial studies of a novel tridentate Schiff base and some lanthanide（III） complexes

A novel potential tridentate Schiff base was prepared by condensing equimolar quantities of 2-hydroxyacetophenone and 2-aminopyrimidine in methanol. This ligand was versatile in forming a series of complexes with lanthanide ions such as La（III）, Pr（III）, Nd（III）, Sm（III）, Gd（III）, Dy（III） and Yb（III）. The ligand and the metal complexes were characterized through elemental analysis, molar conductance, UV-Visible, IR, 1H NMR, and mass spectral studies. The spectral studies indicated that the ligand was coordinated to the metal ion in neutral tridentate fashion through the azomethine nitrogen, one of the nitrogen atoms in the pyrimidine ring and the phenolic oxygen without deprotonation. Thermal decomposition and luminescence property of lanthanum（III） complex were also examined. The X-ray diffraction patterns showed the crystalline nature of the ligand and its lanthanum（III） complex. The DNA cleavage studies of the ligand and the metal complexes were carried out and it was observed that the lanthanum（III） and neo-dymium（III） complexes cleaved the pUC19 DNA effectively. The ligand and the metal complexes were screened for their antibacte-rial activities. The metal complexes were found to be more potent bactericides than the ligand.     

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.     

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

A new stripping agent N, N-dimetbyl-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 0.258nm, 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.     

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.     

Hydrothermal Synthesis and Crystal Structure of Lanthanum Orotate Supermolecule with A Honeycomb Structure Constructed from Mononuclear Molecules via Hydrogen Bonds

A new complex of lanthanum orotate [La（C5H3N2O4）2（OH）（H2O）6 ]·2（C5H4N2O4）·9H2O was synthesized using a hydrothermal method. The crystal structure was determined with help of single crystal X-ray diffraction analysis. The complex crystallized in orthorhombic system, Cmc2（1） space group. In the complex, the center lanthanum （Ⅲ） ion was nine-coordinated with coordination geometry of a distorted monocapped square antiprism, in which two of the nine coordinated oxygen atoms were from two orotate ligands in a monodentate mode, one oxygen atom from a hydroxyl, and the others from six coordinated water molecules. The mononuclear complex [La（C5H3N2O4）2（OH）（H2O）6 ]·2（C5H4N2O4）·9H2O was linked through the hydrogen bonds into an infinite supermolecular honeycomb structure.     

Kinetic Study on the Induced Coordination Reaction of Lanthanum with p-Acetylcarboxylazo

The absorption spectra of p-ACA(p-acetylcarboxylazo)and its complex with lanthanum ionswere determined.The molar ratio of metal to ligand in the complex was estimated to be 1:2.An inductionperiod was found existing in the coordination reaction between La and p-ACA and the effects oftemperature,acidity and ionic strength on the induction period were studied.The reaction mechanism wasdepicted.The rate equation is consistent with the rate law,R=k[La(H_2O)_6~(3+)][H_3O~+],obtained by kineticmethod.Finally the possible geometric structure of this complex was discussed.     

Synthesis and spectroscopic properties of rare earth picrate complexes with a new dinaphthalenelamide

The new ligand N-benzyl-2-{2’-[(benzyl-ethyl-carbamoyl)-methoxy]-dinaphthalene-2-yloxy}-N-ethyl-acetamide(L) and its complexes of rare earth picrates were synthesized.The complexes were characterized by elemental analysis,IR,UV-vis spectra and conductivity measurements.The fluorescence properties of the europium complex in solid state and CHCl3,ethyl acetone,acetonitrile and DMF were investigated.Under the excitation,the europium complex exhibited characteristic emissions of europium.The lowest triplet state energy level of the ligand indicated that the triplet state energy level of the ligand matched better to the resonance level of Eu(Ⅲ) than Tb(Ⅲ) ion.     

Synthesis,characterization and fluorescence properties of a novel rare earth complex for anti-counterfeiting material

A novel ligand with two ester groups,two benzene rings and two carbox yl groups was synthesized. The composition and structure of the ligand were char acterized by the Fourier transform infrared spectroscopy(FT-IR) ,nuclear magnet ic resonance spectrum(NMR) and UV spectrometer. The rare-earth complex with the ligand and 1,10-phenanthroline(phen) was synthesized and structurally charact erized by FT-IR,TG and fluorescent spectrometer. The results showed that the no vel multicarboxyl ligand could efficiently transfer the energy to Eu3+ ions in t he complex and sensitize the luminescence of the rare earth ions,and the comple x could emit strong fluorescence of the rare earth ions.     

Spectra of Solid Rare Earth Complexes RE（C5H8NS2）3（C12H8N2）

The solid complexes RE (C5H8NS2)3(C12H8N2) (RE=La,Pr,Nd,Sm-Lu) were synthesized in absolute ethanol, and were characterized by IR,UV and FS spectra. IR results reveal that the RE^3 coordinated with sulfur atoms of APDC and nitrogen atoms of o-phen. As for UV spectrum of the complexes, energy transfer between o-phen and RE^3 is the primary process, and the main absorption peaks show a slight red shift than that of o-phen; FS spectrum, as a comparison, the complexes Sm (C5H8NS2)3(C12H8N2) and Eu (C5H8NS2)3(C12H8N2) have stronger fluorescence character.     

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), Sin(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.     

Synthesis and fluorescent properties of a novel europium（III） complex with terpyridine-capped poly（ethylene glycol）

Terpyridine-capped poly(ethylene glycol) (PEG) was synthesized as a novel polymeric ligand and rare earth complex was prepared from Eu(NO3)3 and the telechelic macromolecules. The structure of the complex was characterized by 1H NMR, FT-IR, UV-vis and fluores-cence spectroscopy. Strong fluorescent emission of the complex was observed at 593 and 616 nm upon the excitation of 300 nm. The fluo-rescent emission was quenched upon addition of trace amount of diethyl chlorophosphate (DCP). And the observed Ksv values for DCP were measured to be 0.568×103 and 0.89×103 L/mol for quenching at 593 and 616 nm, which indicated the detection limit for DCP was about 0.014 mmol/L. These results showed that the terpyridine-lanthanide complex could be an effective chemosensor with a potential application in the detection of organophosphates.     

Hydrothermal synthesis and structural studies of a new coordination polymer of lanthanum(Ⅲ) with benzene-1,2,4,5-tetracarboxylic acid and 4,4''-bipyridine

A new lanthanum complex formulated as { (bpyH2)[La(btc)(H2O)4(NO3)]·2H2O }n (1) (btcH4=benzene-1,2,4,5-tetracarboxylic acid; bpy=4,4'-bipyridine) was hydrothermally synthesized. The complex was characterized by FT-IR spectroscopy, elemental analysis and X-ray diffraction. X-ray crystal structural analysis revealed that the compound belonged to the monoclinic space group C2/c with cell parameters a= 1.42806(7) nm, b=1.10258(5) ran, c=-1.60333(8) nm and β=101.9400(10)°. The complex was polymeric with La<Ⅲ atoms linked by four O atoms from two carboxylate groups of one benzene-1,2,4,5-tetracarboxylate. The LaⅢ atom was ten coordinated in a distorted tetracapped trigonal prism. In the crystal structure, a wide range of noncovalent interactions consisting of hydrogen bonding (of the types of O-H…O, N-H…O and C-H…O) and ion pairing interactions connected the various components into a supramolecular structure.     

Studies on some lanthanide（Ⅲ） complexes with 4-hydroxyantipyrine

Seven new lanthanide（Ⅲ） complexes with 4-hydroxyantipyrine were synthesized. These complexes were characterized by elemental analysis, molar conductance, magnetic moment measurements, FT-IR, electronic and 1HNMR spectra, X-ray powder diffraction, and thermogravimetric studies. The ligand, 4-hydroxyantipyrine （hap）, contained carbonyl oxygen and hydroxyl oxygen as potential donor sites. On coordination, deprotonation occurred and as a result, hap acted as a monobasic bidentate ligand. A coordination number 6 was assigned to the lanthanide（Ⅲ） ions in these complexes with orthorhombic structure. All the complexes were thermally stable-150℃ and underwent decomposition in three stages with the formation of Ln2O3 as the final residues.