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.

Study on Luminescence Properties of a Novel Rare Earth Complex Eu(TTA)_2(N-HPA)Phen

A novel rare earth complex Eu（TTA）2（N-HPA）Phen （TTA = thenoyltrifluoroacetone, N-HPA = N-phenylanthranilic acid, and phen = 1,10-phenathroline ）, which contains three different ligands, was synthesized. The Eu complex was blended with poly N-vinylcarbazole （PVK） in different weight ratios and spin coated into films. The luminescence properties of films were investigated and energy transfer between PVK and the complex was discussed. Multilayer structural devices consisting of ITO/PVK： Eu （TTA）2 （N-HPA） phen/BCP/Alq3/Al were fabricated with PVK ： Eu （TTA）2（N-HPA） as light-emitting layer. Increasing the concentration of Eu in the PVK thin film would inhibit the emission of PVK to different degrees. Finally, the pure red luminescence of europium（ Ⅲ ） was observed when the doping weight ratio was approximately 1 ： 5, which indicated an effective energy transfer from PVK to rare earth complex.

Study of Electroplex Emission from Organic Electroluminescent Devices with Rare Earth Complex

A novel organic electroluminescent device was made with the structure of ITO/PVK：Tb0.5Eu0.5（TTA）3 Dipy/ BCP/Alq3/Al（a） which utilized the rare earth complex Tb0.5Eu0.5（TTA）3 Dipy as the emitting layer. When it was driven under a direct electric field, 612 nm emission from EU^3＋ and 410 nm emission from PVK were observed. In addition, in the EL spectrum a new peak at 490 nm appeared. From the analysis of different devices, the mechanism of the new emission was studied. It was concluded that the new emission was the electroplex originating from the interface between the ligand （TTA）3Dipy and BCP.

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 electrohiminescence 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.

Self-Assembled Film of Tb^(3+) and Poly(3- Thiophene Acetic Acid) via Layer-by-Layer Complexation Technique and Its Photoluminescence

The layer by layer complexation technique of polymer and metal ion was successfully utilized to fabricate the ultrathin multilayer film of poly(3 thiophene acetic acid (PTAA) and Tb 3+ ion by dipping the substrates alternatively in polymer and Tb 3+ ion aqueous solutions. UV-vis measurement revealed that the absorbance has linearity with the bilayer number from layer to layer and the X ray photoelectron spectrum (XPS) confirmed the existence of Tb 3+ ion. The pH of both the polymer and TbCl 3 solutions influence the thickness dramatically while the concentration of the solutions is not so sensitive. The luminescent spectrum of the complex film shows the characteristic emission of Tb 3+ ion as well as the ligand indicating the formation of the complex.

Synthesis and Photoluminescence of Three Europium (Ⅲ) Ternary Complexes with New Secondary Ligands of Different Structure

Three new 1,10-phenanthroline derivatives, dipyrido (3,2-f: 2,3-h) quinoxaline (DPQN), imidazo (5,6-f)-(1,10)-phenanthroline (IP) and 3-phenyl-imidazo (5,6-f)-(1,10)-phenanthroline (PIP) were designed and synthesized as a secondary ligand to coordinate with europium (Ⅲ) ion while dibenzoylmethane (DBM) was used as the first ligand. The compositions of the ligands and the europium (Ⅲ) ternary complexes were confirmed by elementary analysis, IR and (()~1H-NMR) spectroscopy. The UV-visible absorption spectra, thermal stability, photoluminescence spectra, quantum yield and fluorescence life time of the Eu(Ⅲ) complexes were investigated. The effect of the structure of the secondary ligand on the photoluminescence of the complexes was discussed. The results show that the synthesized Eu(Ⅲ) complexes are good red-emitiing materials for potential application in fabrication of organic electroluminescence devices.

Slow magnetic relaxation and photoluminescence behaviors of dilanthanide complexes bearing N_(8)O_(2)donor macrocyclic ligand

On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule magnets.Therefore,it is necessary to develop reasonable bridging ligands to manipulate the directional assembly of binuclear lanthanide complexes.Herein,we selected the macrocyclic ligand L^(N_(8)O_(2))to build up two new dilanthanide complexes[Ln_(2)(LN_(8)O_(2))(OpyO)_(2)(H_(2)O)2](NO_(3))_(2)(1-Ln,Ln=Dy,Tb;LN_(8)O_(2)=hexamethyl-tetraaza-dioxe-dipyrazolacycloicosaphane-2,9,12,19-tetraene;OpyOH=2-pyridinol-1-oxide).Dynamic magnetic studies show that 1-Dy exhibits slow relaxation behavior under a 1 kOe applied field.Further fitting analysis of relaxation times gives the effective energy barrier of 38.2 cm^(−1),and reveals that the slow magnetic relaxation behavior is dominated by the Orbach and Raman processes.High-resolution luminescence emission spectrum indicates the energy gap of 36.8 cm^(−1)between the ground state and the first excited state,consistent with the magnetic measurement results.1-Tb exhibits brilliant characteristic green light emission under UV light excitation.The absolute quantum yield of 1-Tb is 44.8%,and its first-order fitted decay lifetime is 779.21μs at room temperature.This study provides the way for directional construction of high-performance molecular materials with magnetic and optical dual-function.

Enhanced photoluminescence from porous silicon microcavities by rare earth doping

The photoluminescence(PL) properties of porous silicon microcavities(PSMs) in the visible range at room temperature are improved by doping the rare earth ytterbium(Yb) into PSMs prepared by the electrochemical etching method.It is observed that PSMs doped with the rare earth have an emission band around 630 nm.Compared with the single-layer porous silicon(PS) film,the PSMs doped with Yb have narrower and stronger PL spectrum.

An Approach for Preparation of Porous Silicon/Rare Earth Hybrid——Immersion Method

A simple but effective doping method, immersion method, was presented. Rare earth complexes [Na3Tb（DPA）3·9H2O and Na3Eu（DPA）3·9H2O] were introduced into porous silicon （PS）, where H2DPA is 2,6-dicarboxy pyridine acid. Rare earths were proved to dope into PS effectively by photoluminescence （PL） and X-ray energy dispersive spectroscopy （EDS）. And the prepared hybrid samples of PS/RE were found to emit intense room-temperature red and green luminescence while the luminescence of porous silicon are almost thoroughly quenched.

Co-luminescence properties of terbium ions–benzoic acid–phen complexes doped with europium ions

Series of complexes Eux Tb1-x(BA)3phen(0.01 B x B 0.50)were synthesized by co-precipitation method,BA was used as the carboxylic acid ligand and 1,10-phenanthroline was used as the electrically neutral ligand.The samples were characterized by means of X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),thermal gravimetric analyses and differential scanning calorimetry(TG–DSC),ultraviolet and visible spectrophotometer absorption spectra,and photoluminescence spectra to study the structure,the energy absorption,the thermal,and luminescent properties of the rare earth complexes.The results show that the series rare earth organic complexes are well crystallized and show high thermal stability.The luminescent intensity of europium ion in the complexes increases as terbium ion transfers the absorbed energy to europium ion in the complexes.The emission of terbium ion at 545 nm is not quenched by europium ion but increases with the content of europium ion decreasing.When the x value is 0.01,the fluorescence intensity reaches the maximum as well as the emission intensity of terbium ions at 545 nm and europium ions at614 nm are almost equal.It realizes the co-luminescence phenomenon of terbium ion and europium ion.The series rare earth organic complexes with different colors can be obtained by adjusting the ratio of terbium ion and europium ion.

Organic Light Emitting Devices Based on Terbium Complex

Rare earth complex TbY(m-MOBA)_6(phen)_2·2H_2O was synthesized, which was first used as an emitting material in electroluminescence. The properties of monolayer device with the rate of 1000 r·min^(-1) (70 nm) and the impure concentration of 1∶5 were the best. And the highest brightness of this device reached 21.8 cd·cm^(-2) at a fixed bias of 20 V. Bright green emission can be obtained from the optimized double-layer device, and the highest EL brightness of the device reached 289 cd·m^(-2) at the voltage of 21 V.

Triboluminescence of A New Europate Complex

A new europium (Ⅲ) complex Eu(HFNH) 3Phen (HFNH: 4, 4, 5, 5, 6, 6, 6-heptafluoro-1-(2-naphthyl)hexane-1,3-dione; phen: 1,10-phenanthroline) was synthesized and its triboluminescent phenomenon was observed. Photoluminescence and triboluminescence spectra were successfully determined. The most intense triboluminescent emission originates from the transition of the central Eu 3+ ion from 5D 0 level to 7F 2 level. The triboluminescent spectrum is basically similar to that of photoluminescence, which correlates with the disorders of F atoms.

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.

Photoluminescent and Electroluminescent Properties of Ligand Emitting Y^(3+), La^(3+), Gd^(3+) and Lu^(3+) Complexes

The photoluminescent (PL) and electroluminescent (EL) properties of a series of ligand emitting rare earth complexes (including Y^(3+), La^(3+), Gd^(3+) and Lu^(3+)) were systematically studied. These complexes have the same anionic ligand, 1-phenyl-3-methyl-4-isobutyryl-5-pyrazoloneate (PMIP), and three neutral ligands, triphenyl phosphine oxide (TPPO), 2, 2′-dipyridine (Bipy) and phenanthroline (Phen). Measured with 60 nm thin film of these complexes vaporized in vacuum on quartz substrates, a good regularity in the PL properties was observed. For rational comparison, the same structural EL devices based on these complexes, ITO/PVK (40 nm)/the complex (80 nm)/Mg: Ag (200 nm)/Ag (100 nm), were fabricated. Excluding the exciplex emission happens, the EL luminance usually increases with the increasing of PL efficiency.

Organic Light-Emitting Devices Based on Terbium Complex

Rare earth complex with a structure of [Tb(m-MBA)_3phen]_2·2H_2O was synthesized,which was used as light-emitting material in electroluminescence. The terbium complex was dispersed in poly (N-vinylcarbazole) (PVK) as an emitting layer which is made by spin coating. Two kinds of devices were fabricated with structures: as following device Ⅰ: glass/ITO/PVK: terbium complex/PBD/LiF/Al, and device Ⅱ: glass/ITO/PVK: terbium complex/AlQ/LiF/Al. The photoluminescent (PL) and electroluminescent (EL) behaviors of the devices were investigated. Bright green emission can be obtained from optimized device Ⅱ,and the highest EL brightness of it reaches 140 cd·m (-2) at the voltage of 20 V.

Organic Light-Emitting Device Based on Terbium Complex

A new rare earth complex Tb(p-MBA)_3phen was synthesized, which is first used as an emitting material in organic electroluminescence. By doping it into the conjugated polymer PVK, single-layer and double-layer devices were fabricated with structures: device 1: ITO/PVK∶Tb(p-MBA)_3phen/Al; device 2∶ ITO/PVK: Tb(p-MBA)_3phen/AlQ/LiF/Al. The characteristics of these devices have been investigated. The emission of PVK is completely restrained, and only the pure green emission from Tb^(3+) can be observed in electroluminescence. The optimized device 2 has better monochromatic characteristics with the maximal brightness of 152 cd·m^(-2) at the voltage of 20 V.

Organic Light Emitting Devices Based on Terbium Complex

Rare earth complex Tb（BA）3phen was synthesized, which is first used as an emitting material in electroluminescence. The properties of monolayer device with the swing film rote of 1000 r·min^-1（70 nm） and the weight ratio of 1：5 （PVK：Tb（BA）3phen） are the best. And the highest brightness of this device reached 26.8 cd·cm^-2 at a fixed bias of 21 V. Bright green emission could be obtained from the optimized double-layer device and the highest EL brightness of the device reached 322 cd·m^-2 at the voltage of 22 V.

Electroluminescence Based on Eu_(0.5)La_(0.5)(TTA)_3phen Doped Poly N-Vinylcarbazole

A novel rare earth complex Eu0 5La0.5 （TRA）3phen, displaying electroluminescent property, was synthesized, and monolayer and double-layer devices were fabricated by doping it into poly N-vinylcarbazole. The characteristics of these optimized devices were investigated, and the emitting mechanism was explained through the energy band diagram. Optimized double-layer devices with a turn-on voltage of 6.5 V were achieved. At the current density of 68.48 mA·cm^- 2, the maximum brightness and the current efficiency of the device reached 238.4 cd·m^-2 and 0.35 cd·A^-1, respectively.

一类新型稀土配合物的合成与发光特性研究

合成了一类新型稀土配合物Eu(asprin) 3phen和Tb(asprin) 3phen ,并将其掺杂到导电聚合物PVK中 ,制成结构了为ITO/PVK∶RE配合物 /LiF/Al的电致发光器件。很明显 ,在相同掺杂比例下 ,前者的电致发光中PVK发射所占比例较大 ,而后者的电致发光中PVK的发射几乎全部被覆盖掉了 ,进一步研究发现它们的光致发光中也有同样现象存在 ,这表明具有同等配体的此类铕、铽配合物的特性存在很大差别 ,并对这一差别作了初步讨论。

掺杂镧、钇的铽(Ⅲ)乙酰丙酮三元配合物的合成及荧光性质研究

合成了四个系列稀土掺杂铽乙酰丙酮(Hacac)三元配合物RExTb1-x(acac)3phen和RExTb1-x(acac)3bipy(RE=La,Y;x=0,010,020,030,050,070,090,100;phen1,10邻菲罗啉;bipy2,2’联吡啶)。通过红外光谱、X射线粉末衍射对配合物进行了表征。对各系列配合物进行荧光光谱研究,发现La3+,Y3+对Tb3+离子均有荧光增敏作用,并且La3+>Y3+。当x=01～03,多数掺杂配合物比未掺杂铽三元配合物具有更好的发光性能。