Synthesis,fluorescence properties of Tb(Ⅲ) complexes with novel mono-substituted β-diketone ligands

Two novel pyridine-2,6-dicarboxylic acid derivatives of mono-β-diketone named methyl 6-biphenylacetyl-2-pyridinecarboxylate (MBP) and 6-biphenylacetyl-2-pyridinecarboxylic acid (BAA) and their corresponding binary complexes Tb(MBP)3.6H2O and Tb(BAA)3·6H2O were synthesized. The ligands were characterized by elemental analysis, FT-IR and 1H-NMR, and the complexes were characterized with elemental analysis, FT-IR, 1H-NMR and thermogravimetric and differential thermal analysis(TG-DTA). The investigation of fluorescence properties of the complexes Tb(MBP)3·6H2O and Tb(BAA)3·6H2O showed that the introduction of the biphenyl enlarged the π-conjugated system of the ligands and enhanced the luminescent intensity of the complexes. The Tb(Ⅲ) ion could be sensitized more efficiently by the ligands, in particular, the fluorescence intensity of the complex Tb(BAA)3·6H2O was about 20% higher than that of Tb(MBP)3·6H2O and 30% higher than that of Tb(Ⅲ) complexes with bis-β-diketone-type ligands that we have previously reported.     

Synthesis,characteristic and intramolecular energy transfer mechanism of reactive terbium complex in white light emitting diode

A reactive Tb(III) complex with 2-aminobenzoic acid(2-ABAH) and acrylonitrile(AN) as ligands was synthesized.The structure of the complex was characterized by elemental analysis and Fourier transform infrared spectrometry(FT-IR).The results indicated that the ligands were coordinated with Tb(III) ion.Thermal gravity-derivative thermogravimetric(TG-DTG) analysis indicated that the complex kept stable up to 198 oC.Luminescence properties were investigated by UV-vis absorption spectra and fluorescence spectra.The results suggested that being excited at 361 nm,the complex exhibited characteristic emission of Tb(III) ion,revealing that the complex could be excited by 365 nm ultraviolet chip.The HOMO and LUMO,ΔE(HOMO-LUMO),molecular frontier orbital,and the singlet state and triplet energy state levels of the ligands were calculated at the B3LYP/6-31+G(d) level.The results indicated that intramolecular energy transfer mechanism followed Dexter exchange energy transfer theory.Both the calculation for excited state of ligand and energy transfer mechanism could provide the theoretical basis for the design of high luminescent materials of rare earth complexes with organic ligands.     

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 luminescent properties of novel pyrazolone rare earth complexes

A novel pyrazolone pyridine-containing ligand,2,6-bis(1-phenyl-4-ethoxycarbonyl-5-pyrazolone-3-yl)pyridine (H2L) was de-signed and synthesized from pyridine-2,6-dicarboxylic acid (1),and its Eu(III) and Tb(III) complexes were prepared.The ligand and com-plexes were characterized in detail based on FT-IR spectra,1H NMR,elemental analysis and thermal analysis,and the formula of Ln2L3·4H2O (Ln=Eu or Tb) of rare earth complexes was confirmed.The UV-vis absorption spectra and photoluminescence properties of the complexes were investigated,which showed that the Eu(III) and Tb(III) ions could be sensitized efficiently by the ligand (H2L) and emit the photolumi-nescence with high intensity,narrow half-peak width,and monochromic light.The results indicated that the complexes showed potential as excellent luminescent materials.     

Synthesis, characterization and properties of some rare earth complexes with 2,6-pyridine dicarboxylic acid and α-Picolinic acid

Five novel ternary complexes were synthesized by the rare earth with 2,6-pyridine dicarboxylic acid andα-picolinic acid.These complexes were characterized by elemental analysis,molar conductivity,FT-IR,UV-Vis,Raman,TG-DTA and XRD.The general formula of the complexes was[RE(DPA)(L α )(H2O)]·2H2O(RE=Pr 3+ ,Nd 3+ ,Sm 3+ ,Eu,Er 3+ ;DPA=2,6-pyridine dicarboxylic acid;L α =α-picolinic acid). The investigation of fluorescence properties of the Eu-complex showed that the Eu(III)ion could be sensitized efficiently by the ligand to some extent.The antibacterial activity test indicated that all the five complexes exhibited antibacterial ability against Escherichia coli and Staphylococcus aureus with broad antimicrobial spectrums.     

Synthesis and fluorescence properties of Eu（Ⅲ）, Tb（Ⅲ） and Sm（Ⅲ） with β-diketone and 2,2＇- bipyridine

Three new rare earth ternary complexes,RE(PPP)3bpy(RE=Sm 3+ ,Eu 3+ ,Tb 3+ ),were synthesized by the reaction of 1-phenyl-3-(p-phenylethynylphenyl)-1,3-propanedione(HPPP)and 2,2′-bipyridine(bpy)with rare earth chloride RECl3,respectively,in alcohol solution. The compositions were characterized by means of infrared(IR)spectra,chemical analysis,elemental analysis,and thermodynamic analysis.Luminescent properties of the three complexes were studied.At room temperature,under UV light excitation,the Sm 3+ ,Eu 3+ and Tb 3+ complexes exhibited characteristic emission of the central ions.The fluorescence spectra showed that the fluorescence emission intensity of Eu 3+ complex was the strongest.The narrow strongest emission band of Eu 3+ complex was considered to be a valuable material with bright red fluorescence.     

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 Tb3+ with a life time of 0.98914 ms.     

Synthesis, characterization, and anticancer properties of rare earth complexes with Schiff base and o-phenanthroline

Five novel ternary complexes of the rare earth ions with o-phenanthroline（Phen） and Schiff base salicylaldehyde L-phenyla- lanine（KHL） were synthesized in ethanol. Their compositions were characterized by elemental analysis, molar conductance, ^1H NMR, FT-IR, and Raman spectra. The formulas of the complexes were verified to be RE（L）（Phen）Cl（H2O） （RE=La^3＋, Ce^3＋, Nd^3＋, Er^3＋, and Gd^3＋; L=Schiff base salicylaldehyde L-phenylalanine; phen=o-phenanthroline）. Methyl thiazolyl tetrazolium （MTT） colorimetry and flow cytometry were used to test the anticancer effect of the complexes with K562 tumor cell. The research showed that the complexes could inhibit K562 tumor cell＇s growth, generation, and induce apoptosis. The inhibition ratio was accelerated by increasing the dosage, and it had significant positive correlation with the medication dosage.     

Fluorescence and Judd-Ofelt analysis of rare earth complexes with maleic anhydride and acrylic acid

Two kinds of Eu-complexes, Eu(TTA)2(Phen)(AA) and Eu(TTA)2(Phen)(MA) (HTTA=2-Thenoyltrifluoroacetone, Phen=1,10- phenanthroline, AA=acrylic acid, MA=Maleic anhydride), which combined the excellent fluorescence properties of Eu(TTA)2(Phen)(H2O) and the reactivity of acrylic acid and maleic anhydride with radicals, were synthesized. The two complexes were characterized by elemental analysis, infrared (IR) spectra, and X-ray photoelectron spectroscopy (XPS). Based on the data shown from the fluorescent spectra of the Eu-MA and Eu-AA complexes, the ?λ (λ=2 and 4) experimental intensity parameters were calculated. The results demonstrated that the ?2 intensity parameters for the two complexes were smaller than those for the Eu(TTA)2(Phen)(H2O) complex, indicating that a less symmetri- cal chemical environment existed in the complexes. It implied that the radiative efficiency of the 5D0 of these two complexes could be en- hanced by ligand of MA and AA, respectively. The luminescent lifetime of the Eu-AA (τ=7.26×10–4 s) or Eu-MA complex (τ=8.12×10–4 s) was higher than that of the Eu(TTA)2(Phen)(H2O) complex, which was attributed to the substitution of the water molecule (H2O) in Eu(TTA)2(Phen)(H2O) by the MA or AA ligand.     

Synthesis,characterization and fluorescence properties of a novel rare earth complexes with a multi-branched ligand and 1,10-phen

A novel multi-branched ligand with multiple ester groups,multiple benzene rings and multiple carboxyls was synthesized.The composition and structure of the ligand were characterized through the Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance spectrum(1H NMR) and UV spectrometer.The composition and fluorescence properties of rare earth complexes with the ligand and 1,10-phenanthroline(phen) were researched via FT-IR,EA and fluorescent spectrometer.The results presented that the resulting complex had strong characteristic fluorescence spectrum of the rare earth ions,which was attributed to the synergistic effects of the ligand,phen,and rare earth ion.     

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.     

Synthesis,crystal structures of novel complexes of rare earth with norfloxacin,interaction with DNA and BSA

Three novel rare earth complexes [N(CH 3) 4 ][Ln(NF) 4 ]·6H 2 O(Ln=Nd(III)(1),Sm(III)(2),Ho(III)(3)) were synthesized using hydrothermal method from norfloxacin HNF=1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid,C 16 H 18 FN 3 O 3),imidazole and rare earth nitrates.The complexes were characterized by elemental analysis,FT-IR,TG-DTG and X-ray single crystal diffraction.Each rare earth ion was eight-coordinated with carboxyl-O atoms and keto-O atoms from norfloxacin.Four of the norfloxacin ions acted as bidentate chelate group took part in the coordination with rare earth ion.The structures of complexes were tetragonal system with space group I4 1 /acd,which were allomerism.The interaction between complex 1 and DNA was studied by electronic absorption spectra and fluorescence spectroscopy.The binding interaction between the complex 1 and bovine serum albumin(BSA) was studied by fluorescence spectroscopy.The complex 1 bound to DNA by the mode of partial intercalation.Complex 1 had a strong ability to quench the fluorescence from BSA.The complex interaction was mainly a static quenching process with BSA together with formation of two binding sites.     

Preparation and characterization of rare earth fluorescent anti-counterfeiting fiber via sol-gel method

A benzoic acid rare earth(Tb) complex was synthesized and characterized.The excitation and emission spectra of the complex were investigated,and then pure organic complex was incorporated with inorganic matrices(SiO2) through sol-gel method.The composition and structure of the hybrid complex was characterized through the IR spectra,TG,TEM and fluorescent spectrometer.Furthermore,the polypropylene(PP) fluorescent fiber with the organic-inorganic hybrid was prepared by melt spinning.The fluorescent and mechanical properties of the fiber were also tested.The results showed that after sol-gel coating the average particulate dimension of the hybrid rare earth complex was less than 100 nm and thermal stability was improved.Meanwhile,the fiber possessed excellent fluorescent and mechanical properties,which could be used as a candidate applied to excellent fluorescent anti-counterfeiting fiber.     

Synthesis,Characterization and Thermal Decomposition Behaviour of Tri-aquo Lanthanum(Ⅲ)Malonate Bimalonate

A new complex of malonic acid with lanthanum,La(Hmal)·(mal)·3H_2O,was synthesizedand characterized by elemental analysis and IR spectra.The thermal decomposition process and their kineticparameters n and E_a were studied by means of TG and DTG.All of the intermediate and end productswere determined and characterized by the mass loss in TG curve,elemental analysis and IR spectra.     

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,crystal structures and characterization of a pair of Tb~Ⅲ-based enantiomers

A pair of novel TbIII-based enantiomers,[Tb(dbm)3·LSS] (1) and [Tb(dbm)3·LRR] (2) (where LSS=(+)-4,5-pinene bipyridine,LRR= (–)-4,5-pinene bipyridine,dbm=dibenzoylmethanate),were synthesized and characterized based on single crystal X-ray diffraction,elemental analysis,FT-IR,TG and CD spectra.X-ray diffraction analysis showed that both the complexes crystallized in monoclinic crystal system with P21 chiral space group.The TbIII ion was eight-coordinated by six O atoms of three dbm ligands and two N atoms fr...     

Cs(ATZ)化合物的合成及表征

A new compound of Cs (ATZ) was synthesized by reaction of CsOH aqueous solution with 5-aminotetrezole. This compound was identified by C, H and N elemental analysis and quantitative analysis of Cs atom. The molecular formula is Cs (ATZ). The physicochemical properties were characterized by FTIR, Raman spectroscopy and X-ray power diffraction and the peaks of FT-IR were also assigned.     

Intercalation Assembly, Characterization and Luminescent Properties of Novel Supramolecular Composite Materials, Tb （ Ⅲ ） Complex with Tetrapodal Ligand- Montmorillonite

Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.     

Hydrothermal syntheses and characterization of three lanthanide coordination complexes constructed by 2,2’:6’,2’’-terpyridine and 2,2’-biphenyldicarboxylic acid

Two 1D coordination polymers [Ln2(dpdc)3(tpy)2·H2O]n [Ln=Nd 1, Yb 2, H2dpdc=2,2’-biphenyldicarboxylic acid and tpy= 2,2’:6’,2’’-terpyridine] and one dinuclear complex Er2(dpdc)2(Hdpdc)2(tpy)2 3 were obtained via hydrothermal reactions and determined by X-ray diffraction analysis. The crystal structure data of 1 and 2 revealed that two coordination polymers were isostructural and possessed a 1D chain framework consisting of eight-coordinated Ln(III) centers. In the asymmetric unit, the two Er(III) ions in 3 were both nine-coordinated and had similar coordination environments. The Er(III) ions were bridged by dpdc2-ligands into dinuclear structures. The complexes were also characterized by IR spectra and thermogravimetric analysis. The solid fluorescence of 1 and 3 was also investigated at room temperature.     

Synthesis and structure of a praseodymium (Ⅲ) complex with carboxylate ligand:A thermal and spectroscopic study

One Pr(Ⅲ) lanthanide ion complex was initially synthesized and characterized by TGA-DSC in air atmosphere, as well as characterized by CHN elemental analysis, defining the stoichiometric ratio as Pr(DMBz)_3. The gaseous products evolved during the thermal decomposition were also monitored in N_2 atmosphere employing TGA/FT-IR system. A crystal structure is obtained by state-of-the-art powder X-rays diffraction methods measured in conventional laboratory equipment and refined by the Rietveld method, which defined it as a monoclinic system of the space group P2_1/C with a polymeric crystal structure, [Pr(DMB_Z)_3]_n. FT-IR theoretical spectrum and time-dependent density functional theory(TD-DFT) were calculated from TGA-DSC and crystalline system data. The experimental and theoretical FT-IR spectra present a high correlation degree when the main stretching bands are compared, while the energy transfer(HOMO — LUMO) in their neighborhoods suggests the main contributions of the light-emitting states.