Synthesis and thermal characterization of luminescent powers of terbium(III) with mixed ligands

This work deals with the synthesis and thermal decomposition of complexes of general formula: Ln(beta-dik)(3)L (where Ln=Tb(+3), beta-dik=4,4,4-trifluoro-1-phenyl-1,3butanedione(btfa) and L=1,10-fenantroline(phen) or 2,2-bipiridine(bipy). The powders were characterized by melting point, FTIR spectroscopy, LTV-visible, elemental analysis, scanning differential calorimeter(DSC) and thermogravimetry(TG). The TG/DSC curves were obtained simultaneously in a system DSC-TGA, under nitrogen atmosphere. The experimental conditions were: 0.83 ml.s(-1) carrier gas flow, 2.0 +/- 0.5 mg samples and 10 degrees C.min(-1) heating rate. The CHN elemental analysis of the Tb(btfa)(3)bipy and Tb(btfa)(3)phen complexes, are in good agreement with the expected values. The IR spectra evinced that the metal ion is coordinated to the ligands via C=O and C-N groups. The TG/DTG/DSC curves of the complexes show that they decompose before melting. The profiles of the thermal decomposition of the Tb(btfa)3phen and Tb(btfa)3bipy showed six and five decomposition stages, respectively. Our data suggests that the thermal stability of the complexes under investigation followed the order: Tb(btfa)(3)phen < Tb(btfa)(3)bipy.

Peptide-lanthanide interactions. Crystal structure of a europium(III)-triglycine complex

Crystals of Eu-(Gly-Gly-Gly).(H2O)5.(ClO4)3 are triclinic, spacegroup P1BAR with a = 9.123 (2), b = 11.185 (5), c = 11.426 (2) angstrom; alpha = 90.79 (2), beta = 98.08 (1), gamma = 98.57 (2)-degrees; Z = 2. The europium cation is surrounded by four oxygens from three different peptide units and four oxygens from water molecules. The geometry around the metal is a distorted bi-capped trigonal prism. The peptide backbone conformation in this complex is compared with those in the free peptide and in various metal complexes. Considerable differences are observed between Eu(III) and Ca(II) complexes of triglycine. (C) Munksgaard 1994.

Enhancing the photocytotoxic potential of curcumin on terpyridyl lanthanide(III) complex formation

Lanthanide(III) complexes Ln(R-tpy)(cur)(NO3)(2)] (Ln = La(III) in 1, 2; Gd(III) in 5, 6) and Ln(R-tpy)(scur)(NO3)(2)] (Ln = La(III) in 3, 4; Gd(III) in 7, 8), where R-tpy is 4'-phenyl-2,2':6',2 `'-terpyridine (ph-tpy in 1, 3, 5, 7), 4'-(1-pyrenyl)-2,2':6',2 `'-terpyridine (py-tpy in 2, 4, 6, 8), Hcur is curcumin (in 1, 2, 5, 6) and Hscur is diglucosylcurcumin (in 3, 4, 7, 8), were prepared and their DNA photocleavage activity and photocytotoxicity studied. Complexes La(ph-tpy)(cur)(NO3)(2)] (1) and Gd(ph-tpy)(cur)(NO3)(2)] (5) were structurally characterized. The complexes in aqueous-DMF showed an absorption band near 430 nm and an emission band near 515 nm when excited at 420 nm. The complexes are moderate binders to calf-thymus DNA. They cleave plasmid supercoiled DNA to its nicked circular form in UV-A (365 nm) and visible light (454 nm) via O-1(2) and (OH)-O-center dot pathways. The complexes are remarkably photocytotoxic in HeLa cells in visible light (lambda = 400-700 nm) and are non-toxic in the dark. FACScan analysis of the HeLa cells treated with 2 and 4 showed cell death via an apoptotic pathway. Nuclear localization of 1-4 is evidenced from confocal imaging on HeLa cells. The hydrolytic instability of curcumin gets significantly reduced upon binding to the lanthanide ions while retaining its photocytotoxic potential.

Ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complex-functionalized mesoporous SBA-15 materials that emit in the near-infrared range

The tertiary lanthanide complexes [Ln(hfth)(3)phen] (Ln=Er, Nd, Yb, Sm) and [Pr(tfnb)(3)phen] have been Successfully covalently attached in the ordered SBA-15 mesoporous materials via a functionalized 1,10-phenanthroline group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (Phen-Si). The derivative materials [denoted as Ln(hfth)(3)phen-S15 and Pr(tfnb)(3)phen-S15; Ln=Er, Yb, Nd, Sm; hfth=4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb=4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate] were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and N-2 adsorption/desorption.

Four New Lanthanide-Nitronyl Nitroxide (Ln(III)=Pr-III, Sm-III, Eu-III, Tm-III) Complexes and a Tb-III Complex Exhibiting Single-Molecule Magnet Behavior

Five new complexes based on rare-earth-radical [Ln(hfac)(3)(NIT-5-Br-3py)](2) (Ln=Pr (1), Sm (2), Eu (3), Tb (4), Tm (5); hfac = hexafluoroacetylacetonate; NIT-5-Br-3py = 2-(4,4,5,5-tetramethyl-3-oxylimidazoline-1-oxide)-5-bromo-3-pyridine) have been synthesized and characterized by X-ray crystal diffraction. The single-crystal structures show that these complexes have similar structures, in which a NIT-5-Br-3py molecule acts as a bridging ligand linking two Ln(III) ions through the oxygen atom of the N-O group and nitrogen atom from the pyridine ring to form a four-spin system. Both static and dynamic magnetic properties were measured for complex 4, which exhibits single-molecule magnetism behavior.

Bifunctional magnetic-optical nanocomposites: Grafting lanthanide complex onto core-shell magnetic silica nanoarchitecture

Anew class of bifunctional architecture combining the useful functions of superparamagnetism and terbium complex luminescence into one material has been prepared via two main steps by a modified Stober method and the layer-by-layer (LbL) assembly technique. The obtained bifunctional nanocomposites exhibit superparamagnetic behavior, high fluorescence intensity, and color purity. The architecture has been characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), UV-vis absorption and emission spectroscopy, X-ray diffraction, and superconducting quantum interference device (SQUID) magnetometry.

Lanthanide complex/polymer composite optical resin with intense narrow band emission, high transparency and good mechanical performance

Novel composite resins possessing good luminescent properties have been synthesized through a free radical copolymerization of styrene, alpha-methylacrylic acid and the binary or ternary complexes of lanthanide ions (Eu3+ and Tb3+). These polymer-based composite resins not only possess good transparency and mechanical performance but also exhibit an intense narrow band emission of lanthanide complexes under UV excitation. We characterized the molecular structure, physical and mechanical performance, and luminescent properties of the composite resins. Spectra investigations indicate that alpha-methyl-acrylic acid act as both solubilizer and ligand. Photoluminescence measurements indicate that the lanthanide complexes show superior emission lines and higher intensities in the resin matrix than in the corresponding pure complex powders, which can be attributed to the restriction of molecular motion of complexes by the polymer chain networks and the exclusion of water molecules from the complex. We also found that the luminescence intensity decreased with increasing content of alpha-methylacrylic acid in the copolymer system. The lifetime of the lanthanide complexes also lengthened when they were incorporated in the polymer matrix. In addition, we found that the relationships between emission intensity and Tb (Eu) content exhibit some extent of concentration quenching.

Green electroluminescence generated from the thin film based on a soluble lanthanide complex

Electroluminescent (EL) devices based on a soluble complex Tb(MDP)(3) [Tris-(monododecyl phthalate)Terbium] doped with poly (N-vinylcarbazole) (PVK), (2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole) (PBD) were fabricated. The device structures of ITO/PVK/PVK:PBD:Tb(MDp)(2)/Aiq(3)/Al and ITO/PVK:PBD:Tb(MDP)(3)/Alq(3)/Al were employed. The Tb(MDP), as emissive layer was spin-coated. The EL cell exhibited characteristic emission of terbium ion. (C) 2000 Elsevier Science S.A. All rights reserved.

Nanostructured hybrid organic-inorganic lanthanide complex films produced in situ via a sol-gel approach

Communication: Nanostructural hybrid organic-inorganic lanthanide complex films were prepared in situ by use of a novel sol-gel precursor containing pendant triethoxy-silyl and carboxyl groups (see Figure). The resulting transparent and crack-free films gave rise to strong red or green emission, even at low lanthanide ion concentration. Phase separation and lanthanide ion aggregation were controlled at the nanoscale.

Synthesis of the first mono(cyclopentadienyl)lanthanide Schiff base complex bearing C-2-symmetric tetradentate ligand: crystal structure of [(eta(5)-C5H5)Yb(mu-OC20H20N2O)](2)(mu-THF)(THF)

Reaction of YbCl3 with 3 equimolar CpNa (Cp = cyclopentadienide) in THF, followed by treatment with trans-(+/-)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine led to the isolation of first mono(cyclopentadienyl) lanthanide Schiff base complex, [(eta(5)-C5H5)Yb(mu-OC20H20N2O)](2) (mu-THF)(THF) (1). The molecular structure of 1 shows that it is a dimer in which the two [(eta(5)-C5H5)Yb(mu-OC20H20N2O)] units connecting via a bridging THF oxygen and two bridging oxygen atoms from Schiff base ligands. (C) 1998 Elsevier Science S.A.

Bright red electroluminescent devices based on a soluble lanthanide complex Eu(DBM)(3)(phen)

Electroluminescent devices with PVK film doped with Eu(DBM)(3)(phen) and PBD were fabricated. The device structure of glass substrate/indium-tin-oxide/PPV/PVK:Eu(DBM)(3)-(phen):PBD/Alq(3)/Al was employed. The emissive layer was formed by spin-casting method. A sharply red electroluminescence with a maximum luminance of 114.4 cd/m(2) was achieved at 42 V.

Synthesis and X-ray crystal structure of [(eta(5)-C5H5)Sm(mu-OC20H20N2O)](2)(mu-THF)(THF)(2): Mono(cyclopentadienyl)lanthanide complex bearing a C-2-symmetric tetradentate Schiff-base ligand

Cp2SmCl(THF) reacts with 0.5 equivalent disodium salts of trans-(+/-)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine give the title complex [(eta(5)-C5H5)Sm(mu-OC20H20N2O)](2)(mu-THF)(THF)(2) (1). X-ray crystal determination shows that the molecule is a dimer, in which two (eta(5)C(5)H(5))Sm(mu-OC20H20N2O) units are connected via a THF oxygen and two bridging oxygen atoms of Schiff base ligands. The average Sm-C distance is 2.78(7) Angstrom, while those of Sm-O (bridging THF oxygen) and Schiff base oxygens are 2.79(3) and 2.43(4) Angstrom; respectively. (C) 1998 Elsevier Science Ltd. All rights reserved.

Electrochemical studies of a lanthanide heteropoly tungstate/molybdate complex in polypyrrole film electrode and its electrocatalytic reduction of bromate

An electrode modified with a polybasic lanthanide heteropoly tungstate/molybdate complex K10H3[Nd(SiMo7W4O39)(2)] entrapped into polypyrrole (PPy) film, denoted as Nd(SiMo7W4)(2)-PPy, exhibits three couples of two-electron redox waves in pH 1-5 buffer solutions. The redox waves are surface-controlled at lower scan rates and diffusion-controlled at higher scan rates. The effects of pH on the electrochemical behavior of Nd(SiMo7W4)(2) in PPy film were investigated in detail and compared with that of Nd(SiMo7W4)(2) in aqueous solution. The various charge states of PPy during its redox process have peculiar effects on the relationship between pH and formal potentials of Nd(SiMo7W4)(2)-PPy at different acidities. The Nd(SiMo7W4)(2)-PPy cme can remarkably catalyze the electrochemical reduction of bromate with good stability. (C) 1997 Elsevier Science Ltd.

Hydrothermal synthesis and lanthanide doping of complex fluorides, LiYF4, KYF4 and BaBeF4 under mild conditions

The complex fluorides LiYF4, KYF4, BaBeF4 and AYF(4)Eu(x) (A = Li, K) are hydrothermally synthesized at 140-240 degrees C and characterized by powder X-ray diffraction, thermogravimetric analysis, IR spectroscopy, scanning electron microscopy and luminescence measurements.

A novel structure analysis method for lanthanide complex - None paramagnetic shift tri-lanthanide mixture method

A new structure analysis method for lanthanide complexes was proposed, that is, none paramagnetic shift tri-lanthanide mixture method, It was found that the paramagnetic induced shift could be cancelled by mixing three kinds of paramagnetic lanthanide ions in appropriate proportion. As a result, the chelating sites would he seen simplely from the half widths and the relative distances between lanthanide ion and the ligand nucleus could be calculated from the relaxation time (T-1) or the half width. Care should be addressed that the analysis method is suitable for the systems in which intramolecular arrangements and intermolecular ligand exchanges are relatively fasten NMR time scale used.