Synthesis and Photoluminescence Properties of Rare Earth Complexes with 3-Allyl-2, 4-Pentanedione

In order to combine the merits of rare earth organic complexes with excellent material performances of polymers,a polymerizable chelating agent, 3-allyl-2, 4-pentane dione (APD), was synthesized by phase transfer catalysis and its rare earth complexes were prepared. The compounds were characterized by EA, IR and ^1H NMR. Their UV spectra and fluorescence spectra were investigated. The effects of allyl on the luminescence properties of the complexes were studied.The results show that the sensitization of APD is changed by allyl in comparison with that of acetyl acetone (acac), and it becomes an ideal novel ligand of Eu. In addition, intramolecular energy transfer mechanism in the luminescence process in the complexes was also discussed in detail.     

Synthesis and Photophysical Properties of Dy^3＋ and Gd^3＋ Polymeric Complexes with Functionalized Polybenzimidazole Containing β-Diketone Side Group

The polymeric ligand PBIa （functionalized polybenzimidazole containing β-diketone side group） was successfully synthesized via the reaction of polybenzimidazole （PBI） with 3-Br-acetylacetone in DM SO solvent using Nail as the deprotonation reagent. Its corresponding polymeric complexes of Dy^3＋ and Gd^3＋ were prepared and characterized by FT-IR, ^1H NMR, molar conductance measurements, and thermal analysis. The photoluminescence properties and the probable mechanism of the Dy and Gd complexes were studied. The measurement and analysis of the thermal properties showed that these were thermal stable.     

Lanthanide complexes with β-diketones and coumarin derivates:synthesis,thermal behaviour,optical and pharmacological properties and immobilisation

The paper presents the results of the synthesis of complexes of the ty pe Eu(DBM) 3 and Eu(DBM) 3·Q(DBM-dibenzoylmethane,Q-1,10-phenantroline or 4,7-d iphenyl-1,10-phenantroline) and of Tb-and Nd-complexes with the newly-synthesis ed coumarin derivates 3,3’-[(4-chlorphenyl) methylene) bis(4-hydroxy-2H-chromen-2-one) ,3,3’-[(3,5-dimethoxy-4-hydroxy) methylene) bis(4-hydroxy-2H-chromen-2-one) ,etc. Elemental and thermogravimetric analysis,IR,UV,NMR and fluorescence spe ctroscopy and X-ray analysis were applied for characterisation of the complexes. Some peculiarities of the synthetic procedures for both types of complexes were discussed and the influence of the synthetic approach,pH of the reaction mediu m,temperature of synthesis and drying of the complexes on the composition,stab ility and optical properties was reported. The immobilisation of the complexes i n thin films based on sol-gel produced SiO2 and on polymethylmethacrylate was st udied. The optimal conditions for preparation of the matrices(composition of th e starting system,temperature and time of sol aging,etc.) were recommended. Th e film morphology was evaluated by fluorescence,scanning electron and atomic fo rce microscopy. The interaction of the lanthanide ions with the matrices and the influence of their nature,the effect of the in-situ polymerisation and other f actors on photoluminescent excitation and emission spectra and excited state lif e-times of the complexes were followed. The effect of the second ligand on the p hotoluminescence properties of the immobilised diketonates was further elucidate d. Processes involved in the thermal decomposition of the complexes and microcom posites produced on their base were proposed. Preliminary results on the pharmac ological properties of the coumarin complexes reported showed unambiguously high er cytotoxicity of the Nd complex in comparison with that of the respective ligand.     

New luminescent 10-oxybenzoquinolate complexes of rare earth metals

A series of Sc,Y,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Ho,Er,Tm and Yb complexes with oxybenzoquinoline ligands(BQ) was synthesized by the reactions of 10-hydroxybenzo[h]quinoline with cyclopentadienides or tris(trimethylsilyl)amides of rare earth metals.The structure,as well as the photo-and electroluminescent(PL,EL) properties of these complexes in solutions and solid state were studied.In solutions,complexes of sodium and lanthanides exhibit double peaked ligand-centered PL of enol and keto forms of BQ with a...     

Preparation and photoluminescence enhancement of Li＋ and Eu3＋ co-doped YPO4 hollow microspheres

Li+ and Eu3+ co-doped YPO4 hollow microspheres were successfully synthesized by a sacrificial template method using polystyrene (PS) as template. Techniques of X-ray diffraction (XRD), scanning electron microscopy (SEM), as well as transmission electron microscopy (TEM) were employed to characterize the as-synthesized sample. Furthermore, the photoluminescence (PL) characterization of the Li+ and Eu3+ co-doped YPO4 microsphere was carried out and the effects of the doping concentration of Li+ and Eu3+ active center concentration as well as calcination temperature on the PL properties were studied in detail. The results showed that the incorporation of Li+ ions into the YPO4 :Eu3+ lattice could induce a remarkable improvement of the PL intensity. The highest emission intensity was observed with the compound of 5%Li+ and 5%Eu3+ co-doped YPO4 , whose brightness was increased by a factor of more than 2.2 in comparison with that of the YPO4 :5%Eu3+.     

Complexation of N＇- [1-（3-aminophenyl）ethylidine] isonicotinohydrazide with La3＋, Pr3＋, Nd3＋, Sm3＋, Eu3＋ and Gd3＋ ions and associated thermodynamics

A novel Schiff base N′-[1-(3-aminophenyl)ethylidine]isonicotinohydrazide was prepared and its complexation behavior towards some selected lanthanides had been studied employing pH-metric and calorimetric titration and spectral techniques. pH-metric studies were carried out for the trivalent La, Pr, Nd, Sm, Eu, and Gd complexes in 30% aqueous-dioxane medium at constant ionic strength of 0.05 mol/L NaClO4 and at different temperatures of 293, 303 and 313 K. The proton-ligand formation constants of the ligand indicated the presence of only one dissociable proton while the metal-ligand formation constants were compatible with the formation of 1:1 Ln(Ⅲ) complexes. The sta-bility of the complexes followed the order: La3+Gd3+, showing a break at gadolinium. The thermodynamic parame-ters, ΔG, ΔH and ΔS associated with protonation and complexation reactions were negative which suggested that all reactions were exother-mic and enthalpy-driven. Isothermal calorimetric studies of Gd3+-aeINH systems at 303 K also showed exothermic nature of the complexation reaction and formation of 1:1 complex in agreement with the pH-metric data. Formation of 1:1 complexes was confirmed by the characteriza-tion of Nd(Ⅲ) complex. A seven coordinated geometry was assigned for the complex based on its elemental and spectral data.     

Structural and optical properties of pillared Eu3+-containing layered double hydroxides intercalated by 2- to 12-carbon aliphatic dicarboxylates

While the versatile composition of layered double hydroxides(LDHs)allows the introduction of almost any polyvalent cation in their structure,the exchangeable negatively charged ions intercalated between the plates increase their vast range of functionalities.Here we report on the preparation and optical properties of pillared Eu³⁺-substituted ZnAl LDHs intercalated by aliphatic dicarboxylates:-OOC-(CH₂)_n-2-COO-.The basal distance in these materials is dependent on the size and packing of the intercalated anions.By varying the number(n)of carbon atoms in the aliphatic chain from 2 to 12,the interlayer gallery of these ZnAlEu LDHs is considerably expanded from 0.9 to 2.1 nm.In the interlayer gallery,the aliphatic dicarboxylates form a monolayer,with the aliphatic chain inclined by an angleα≈63°with the hydroxide layers.The carbon atom in the COO-group is 0.43 nm far from the metal plane,showing that these carboxylates are not grafted in the brucite-like layers.These LDHs are thermally stable up to around 150℃,after which dehydroxylation of the hydroxide layers is observed.The Judd-Ofelt intensity parameters were obtained and compared to the Eu³⁺-containing complexes with the same ligand series indicating a more symmetrical and less polarizable chemical environment around the rare earth ion.     

Lanthanide amino acid Schiff base complexes： synthesis, spectroscopic characterization, physical properties and in vitro antimicrobial studies

Complexes of La(Ⅲ),Nd(Ⅲ),Gd(Ⅲ),Sm(Ⅲ),and Ce(Ⅳ) were synthesized with Schiff base [(3,5-di-tert-butyl-2-hydroxybenzyl) amino] acetic acid(H 3 L).The ligand and its complexes were synthesized and characterized based on the following analysis:elemental analyses,FAB-mass,molar conductance measurements,magnetic measurement,UV-visible,IR,and NMR spectral studies.The spectral data revealed that the ligand acted as a neutral tridentate coordinating to metal ion through ONO donor sequence.Thermal degradation studies of the ligand and its complexes showed that the previous lanthanide complexes were more thermally stable than the ligand itself.The Schiff base and its complexes were screened for their antibacterial(Escherichia coli,Staphylococcus aureus) and antifungal(Aspergillus flavus and Candida Albicans).     

Syntheses and Characterization of Binuclear Complexes Tb（1-x）Eux（TTA）3 Phen

Rare earth ternary complexes Tb1-xEux（TTA）3Phen（x=0,0.25,0.5,0.75,1.0）were synthesized and characterized by DTA-TG,XRD and infrared（IR）.The photophysical properties of these complexes were studied in detail using ultraviolet absorption spectra and fluorescent spectra.Ultraviolet absorption showed that the energy absorption of the complexes mostly came from ligands.Infrared spectra of Tb1-xEux（TTA）3Phen complexes were similar to the pure complexes.TG curves proved that the complexes were stable.Tb3＋ emission was almost quenched and the Eu3＋ emission was enhanced by codoping the complexes.The Tb3＋ ion acted as an energy transfer bridge that helped energy transfer from poly（N-vinylcar-bazole（PVK）to Eu3＋.In addition,their PL and EL properties were systematically studied.     

Facile sol-gel combustion synthesis and photoluminescence enhancement of CaZrO3：Sm3＋ nanophosphors via Gd3＋ doping

CaZrO3:Sm and CaZrO3:Sm,Gd nanophosphors were synthesized by a facile and efficient sol-gel combustion method. Their structure and optical properties were studied. The photoluminesce (PL) results showed that the phosphor could be efficiently excited by irradiation at wavelengths in the visible light region (350-430nm). The CaZrO3:Sm nanophosphor exhibited strong yellow-green, orange and red emissions with peak wavelength centered at 565nm (4G5/2→6H5/2), 601nm (4G5/2→6H7/2) and 645nm (4G5/2→6H9/2), respectively. The incorporation of Gd3+ ions could greatly improve the luminescence intensity. The highest emission intensity was observed with 2mol.% Gd3+ doped CaZrO3:3mol.% Sm powder. The material had potential application in the development of materials for LED’s and other optical devices in the visible region.     

Fabrication of Green Electroluminescent Devices

Ｄｉｓｐｌａｙｓｂａｓｅｄｏｎｏｒｇａｎｉｃｌｉｇｈｔｅｍｉｔｔｉｎｇｄｅｖｉｃｅｓ (ＯＬＥＤｓ)ｈａｖｅｂｅｃｏｍｅｐｏｔｅｎｔｉａｌｒｅ ｐｌａｃｅｍｅｎｔｓｏｆｌｉｑｕｉｄ ｃｒｙｓｔａｌｄｉｓｐｌａｙｓ (ＬＣＤｓ)ｄｕｅｔｏｔｈｅｉｒｗｉｄｅｖｉｅｗｉｎｇａｎｇｌｅ ,ｈｉｇｈｅｒｂｒｉｇｈｔ ｎｅｓｓ,ｅａｓｅｏｆｃｏｌｏｒｔｕｎａｂｉｌｉｔｙ ,ｆａｓｔｒｅｓｐｏｎｓｅｔｉｍｅａｎｄｌｏｗｄｒｉｖｉｎｇｖｏｌｔａｇｅ[1] .Ｔｈｅｇｒｅｅｎｏｒ ｇａｎｉｃＥＬｄｉｓｐｌａｙｕｓｉｎｇｔｒｉｓ(8 ｈ…     

Synthesis and Fluorescence Property of Eu^3 ＋ , Tb^3＋ Perchlorate Complexes with Diphenyl Sulfoxide and 1,10-Phenanthroline

Eu3 ,Tb3 canemitfluorescenceinconjugatedsystemcontainingorganicligand[1,2 ] ,forexample ,1 ,1 0 phenanthroline ,becauseithasbettercoordina tionabilityandbiggerconjugationsystem ,soitcantransmitenergyeffectivelytoEu3 ,Tb3 ,leadingtofluorescenceemission ,andthestabilityisveryhigh ,butsolubilityisverypoor .Inaddition ,diphenylsul foxidehasbettercoordinationabilityandbiggerconju gationsystem ,too .Soitcanalsotransmitenergyef fectivelytoEu3 ,Tb3 ,resutlinginfluorescencee mission ,andsolubi…     

Luminescent Properties of A Novel Terbium Complex Tb（o-BBA）3（phen）

A novel rare earth complex of terbium ion with 2-benzoylbenzoic acid and 1, 10-phenathroline （Tb（o-BBA）3 （phen）, o-BBA-2-benzoylbenzoic acid, phen = 1, 10-phenathroline） was used as an electroluminescent material for the first time. The Tb complex was blended with poly（N-vinylcarbazole） （PVK） in different weight ratios and spinn to coated into films （noted as PVK ：Tb films）. The photoluminescence （PL） properties of films were investigated and the optimum weight ratio between PVK and Tb（o-BBA）3（phen） was found to be 3：1. Monolayer devices with the structure ITO/PVK： Tb/AI were fabricated and emitted green light, which was characteristic of Tb^3＋ emission. The results show that mecha- nisms for PL and EL are different. The PL is considered to be caused because of energy transfer and direct excitation to the Tb（o-BBA）3（phen） molecule, while EL is mainly on charging trapping.     

Complexes of carboxymethylcellulose in water. Part 2. Co2+ and Al3+ remediation studies of wastewaters with Co2+, Al3+, Cu2+, VO2+ and Mo6+

The properties of carboxymethylcellulose (CMC) complexes and Co²⁺ and Al³⁺ are reported in this work. The complexing power of CMC was greater to Al³⁺ than to Co²⁺, although it was not possible to determine some of the equilibrium constants. The infrared (IR) spectroscopy and thermal analysis helped in showing the existence of these complexes in the solid state. The films observed by scanning electron microscopy (SEM) provided a certainty that the chains of the biopolymer were not extensively broken by the use of strong mineral acid employed in some of the experimental steps of this study.Two water solutions — bidistilled and deionized water and an Iraí River, Curitiba, PR (Brazil) sample — were obtained by adding metal salts of Al³⁺, Co²⁺, Cu²⁺, Mo⁶⁺(initially in the form of molybdate) and VO²⁺ to which CMC was later added as a remediation agent. At different times, aliquots of those water samples were analyzed for their metal contents and showed ability to sequester different percentages of each of the metal ions, therefore, rendering the water samples within the Brazilian and Spanish standards for potable water (varying from < 0.3 to 5 mg/L depending on toxicity). The CMC complexes could be recovered by mechanical removal at the pH where these complexes are not very soluble. This process can be applied to municipal wasterwater treatment plants as CMC is a more cost-effective and non toxic alternative material than commercial employed alum. The metals can be recycled after the decomplexing process from the recovered solid complexes and with the additional benefit of using CMC that it will leave no trace of Al³⁺ ions in the water rising from the use of alum.     

Photoluminescence and Electroluminescence Studies on Tb-Doped Silicon Rich Oxide Materials and Devices

Light emitting diode (LED) compatible with sili-con-based integrated circuit (IC) has been a highlydesirable candidate for optical interconnections .It isalso economically desirable to replace expensive III-VLEDs with low-cost ,silicon-based devices . Unfortu-nately,it has long been believed that crystalline sili-conis a poor light emitting material because of its na-ture of indirect bandgap . With the discovery of strongPL from porous silicon[1],the understanding of thelight emitting pr…     

Combustion synthesis of Ce~（3＋）, Eu~（3＋） and Dy~（3＋） activated NaCaPO_4 phosphors

The preparation of NaCaPO4 doped with rare earth (RE) ions Ce3+, Eu3+ and Dy3+ by combustion method was described. Under UV excitation (251 nm) of NaCaPO4:Ce3+ showsd emission (367 nm) in UV range. When NaCaPO4:Dy3+ phosphor was excited at 349 nm, the emission spectrum showed intense bands at 482 nm (blue) and 576 nm (yellow). In Eu activated NaCaPO4 phosphor, the emission spectrum showed a dominant peak at 594 nm (orange) while others were at 614 and 621 nm (red) when excited at 393 nm. The prepared phosph...     

Synthesis, Characterization and Antibacterial Properties of Rare Earth (Ce3+, Pr3+, Nd3+, Sm3+, Er3+)Complexes with L-Aspartic Acid and o-Phenanthroline

Five novel ternary complexes of rare earth ions with L-Aspartic acid (Asp) and o-phenanthroline (Phen) were synthesized in ethanol aqueous solution. Their compositions were characterized by elemental analysis, molar conductance, FT-IR, Raman, UV-VIS and TG-DTA. The compositions of the complexes were confirmed to be: RE(Asp)3PhenCl3·3H2O (RE: Ce3 , Pr3 , Nd3 , Sm3 , Er3 ). The antibacterial activity test shows that all these complexes exhibit excellent antibacterial ability against Escherichia coli, Staphylococcus aureus and Candida albicans. The antimicrobial spectrum of the complexes are broad.     

Upconversion of Er3+ Ions in LiKGdF5∶Er3+, Dy3+ Single Crystal Produced by Infrared and Green Laser

The upconversion fluorescence of Er3 ions in LiKGdF5∶Er3 , Dy3 single crystal was studied under 785, 514.5, and 980 nm laser excitation. With the laser excitation set at 785 nm, strong green (centered at 543 nm) upconversion emissions, as well as weak red (651 nm), violet (406 nm), and blue (470 nm) upconversion emissions were obtained. With 514.5 nm laser excitation, violet (406 nm) and blue (470 nm) upconversion emissions were observed. Under 980 nm laser excitation, strong green (543 nm) and weak red (651) emissions were also obtained. The laser power dependence of the upconverted emissions was investigated to understand the upconversion mechanism. The excited state absorption (ESA) and the energy transfer (ET) processes were discussed as the possible mechanisms for all upconversion emissions.