铽配合物Tb(o-BBA)3(phen)有机电致发光研究

合成了一种新的稀土配合物邻苯甲酰苯甲酸-1，10-菲罗啉-铽（Tb（o-DDA）3（phen））并用于有机电致发光。研究了Tb（o-DDA）3（phen）与PVK混合薄膜的光敛发光特性，找出了PVK：Tb的最佳比例为3：1。制备了结构为ITO／PVK：Tb／Al的单层电致发光器件，得到了铽离子的特征光谱，其电流-电压特性（I-V）在一定电压范围内符合空间电荷限制电流机制。研究结果表明稀土铽配合物Tb（o-BBA）3（phert）掺杂PVK体系的光致发光是源于PVK到Tb配合物的能量传递及稀土Tb配合物的直接激发两种作用机制，而电致发光以载流子俘获为主。     

稀土配合物Tb(p-MBA)3phen的有机电致发光

合成了一种新型的稀土铽配合物材料Tb(p-MBA)3phen,把它作为发光材料应用于有机电致发光中.把铽配合物掺杂在导电聚合物PVK中采用旋涂法制得发光层,并利用AlQ作为电子传输层制作了单层、双层有机电致发光器件:器件1(ITO/PVK):Tb(p-MBA)3phen/Al;器件2(ITO/PVK):Tb(p-MBA)3phen/AlQ/LiF/Al,得到了纯正的、明亮的Tb3 离子的绿光发射,4个特征峰分别对应着能级5D4到7Fj(j=6,5,4,3)的跃迁,而PVK的发光完全被抑制.研究了两种器件的电致发光性能,并通过选择AlQ的厚度得到了发光性能较好的器件,其最大亮度在20 V时达到152 cd·m-2.     

基于5-芳基-2-巯基噁二唑辅助配体的双核环金属铂配合物的合成及高效电致红光发光器件

设计合成了一种新型的基于5-芳基-2-巯基噁二唑辅助配体的双核环金属铂配合物（dfppy）2Pt2（C8OXT）2,其中dfppy为2-（4,6-二氟苯基）吡啶,C8OXT为5-苯基-2-巯基-1,3,4-噁二唑桥连配体.系统研究了该双核铂配合物（dfppy）2Pt2（C8OXT）2的热稳定性、光物理、电化学及电致发光性能.以（dfppy）2Pt2（C8OXT）2作为客体掺杂到聚合物主体材料中制备了单发光层聚合物电致发光器件.器件展现了饱和的红光发射,其最大发射峰为620nm.当配合物掺杂浓度为8wt%时,器件性能达到最好.其最高外量子效率为8.4%,最高电流效率为4.2cd/A,最大亮度为3228cd/m2.本研究表明,以5-苯基-2-巯基-1,3,4-噁二唑作为桥连配体的双核铂配合物在聚合物器件中能够实现高效红光发射.     

一种含铽单体的合成及其电致发光研究

合成了一种具有聚合活性的含铽配合物单体(Tb(acac)~2(AA)phen),并用红外光谱、元素分析等进行表征。研制了结构为ITO/PVK/Tb(acac)~2(AA)phen/Alq^3/Al的电致发光器件并测定了它的电致发光谱、电流-电压特性、亮度-电压曲线等性能。该器件具有良好的整流特性,其电致发光显示了铽离子的绿光特征发射,并具有较好的单色性。同时,探讨了该器件的电致发光机理。     

苯甲酰水杨酸铽与PVK混合体系的发光特性

合成了一类以苯甲酰水杨酸（benzoyl salicylic acid,BSA)为第一配体，邻菲罗啉（1,10-phenanthroline,Phen)为第二配体的稀土铽配合物，将导电高分子材料PVK引入到配合物中，制成了结构为ITO／PVK：Tb(BSA)3phen/PBD/Alq/LiF/Al电致发光器件，并对该配合物的吸收特性及电致发光和光致发光性能进行了研究，实验数据表明在PVK与Tb(BSA)3phen之间存在着Forster能量传递，该配合物具有很好的光致发光和电致发光性能。本文同时比较了几种不同PVK掺杂浓度对于器件性能的影响。     

稀土配合物的光致和电致发光性能的研究

合成了一种新型的稀土配合物Tb(acac)3dad, 讨论了其光致发光的性质 . 以其为发射层制备了结构为ITO/TPD (50 nm)/Tb(acac)3dad (75 nm)/PBD (50 nm)/Al (400 nm) 的电致发光器件, 该器件的启动电压为7 V, 18 V时得到了最大亮度为62 cd·m -2, 发现器件的电致发光光谱与配合物Tb(acac)3dad的光致发光光谱有明显不同.     

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。     

稀土配合物Tb(3-metho)3phen掺杂的有机电致发光

合成了一种新型稀土配合物Tb(3-metho)3phen，将其掺杂到导电聚合物PVK中改善了配合物的成膜性和导电性，并对掺杂薄膜进行了荧光，电致发光和形貌的研究，实验表明，存在聚合物到稀土配合物的能量传递，利用能量传递我们得到了窄谱带的绿色有机薄膜电致发光器件。     

稀土铽配合物有机电致发光

利用三价稀土铽配合物作为发射层、二胺衍生物(TPD)以及聚乙烯咔唑(PVK)作为空穴传输层制备了有机电致发光器件. 器件的结构为 玻璃衬底/ITO/PVK 或者TPD/Tb3+ 配合物/Al, 其中空穴传输层TPD 和发光层Tb3+-配合物采用热蒸发办法成膜. 而空穴传输层PVK采用旋甩涂敷的方法成膜. 对于以上的两种器件均获得了来自Tb3+ 的窄峰发射, 在直流电压15.4 V驱动下, 器件发光亮度达210 cd·m-2.     

稀土铽配合物TbY(m-MBA)6(phen)2·2H2O的有机电致发光

合成了两种新型稀土配合物[Tb(m-MBA)3phen]2·2H2O和TbY(m-MBA)6(phen)2·2H2O, 将其掺杂到导电聚合物PVK中用于有机电致发光器件的发光层, 这样改善了配合物的成膜特性和导电性质. 用这种搀杂体系分别制作了单层发光器件和以AlQ为电子传输层的双层器件. 研究了这些单、双层器件的电致发光性能, 对比了以[Tb(m-MBA)3phen]2·2H2O为发光层的双层器件和以TbY(m-MBA)6(phen)2·2H2O为发光层的器件, 发现后者效率更高, 为0.88 cd·A-1, 其最大亮度为123 cd·m-2.     

Synthesis and photophysics properties of novel bipolar copolymers containing quinoline aluminum moieties and carbazole segments

A novel polymerizable 8-hydroxyquinoline aluminum (Alq₃) complex monomer and its copolymers (Alq₃/N-vinylcarbazole (NVK)) with different mole fractions of Alq₃ in feed were designed and synthesized. The structure of the Alq₃-complex monomer was characterized by ¹H NMR, FT-IR and elemental analysis, and the bipolar copolymers with various desired Alq₃ loading were characterized by ¹H NMR, FT-IR, elemental analysis, and gel permeation chromatography (GPC). The results indicate that these copolymers have moderate molecular weight as well as good solubility in common organic solvent. Thermal properties measurement and analysis show that these copolymers possess excellent thermal stability and high glass transition temperature (T_g). The photophysics properties of the copolymers were studied by UV–vis and fluorescence spectra. Nearly monochromatic yellow–green emission from Alq₃ was observed in high concentration solution and solid state, showing effective energy transfer characteristic. The results demonstrate that introduction of carbazole as hole-transporting and energy transfer group is a potential method to improve the luminescent performance of the Alq₃-based polymers.     

Study of the luminescence properties of a novel rare earth complex Tb(DPC)22H2O

Rare earth complex Tb(DPC)₂2H₂O was synthesized by introducing Pyridine-2,6-dicarboxylic acid(H₂DPC) as the ligand and characterized by UV, fluorescent and infrared spectra as well as elemental analysis. The complex exhibited ligand-sensitized green emission, and it has the higher sensitized luminescent efficiency and longer lifetime. The effect and mechanism of the ligand (H₂DPC) on the luminescence properties of terbium complex was discussed. In device ITO/PVK/Tb(DPC)₂2H₂O/Al, Tb³⁺ may be excited by intramolecular energy transfer from ligand as observed by electroluminescence. The main emitting peak at 545 nm can be attributed to the transition of ⁵D₄→⁷F₅ of Tb³⁺ ion and this process results in the enhancement of green emission from electroluminescence device.     

Preparation, photo- and electro-luminescent properties of a novel complex of Tb (III) with a tripod ligand

A novel Tb(III) complex TbL (L=tris[2-(2-carboxyphenoxy)ethyl]amine, H3L) was synthesized and characterized by means of elemental analyses, IR spectra, thermal analyses, and molar conductivity measurement. The photoluminescent properties of the complex were investigated. In addition, PVK doping Tb(III) complex was fabricated as the emissive layer by spin-coating and its electroluminescent properties were studied, in which the structure of the device was ITO (indium tin oxide)/PVK (polyvinylcarbazole)/PVK: TbL/PBD (2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole)/LiF/Al. It was indicated that pure green and narrow bandwidth emission at 545nm from photoluminescence of TbL complex film and the organic electroluminescent device is the characteristic emission of Tb(III) ion, and the electroluminescence spectrum of the device was very similar to that of the photoluminescence of TbL complex film. The lowest triplet level of the ligand was calculated from the phosphorescence spectrum of GdL in N,N-dimethyl formamide (DMF) dilute solution determined at 77K, and the energy transfer mechanisms in TbL complex were discussed.     

Anionically Substituted 1,1′,1″‐Methylidynetris[1H‐pyrazole] Ligands for the Formation of Neutral Lanthanide Complexes in Water: Synthesis,Characterization, and Photophysical Properties

The six‐step synthesis of the new podand‐type ligand 6,6′,6″‐[methylidenetri(1H‐pyrazole‐1,3‐diyl)]tris[pyridine‐2‐carboxylic acid] (LH₃) is described. Reaction of LH₃ with LnCl₃ ?6 H₂O (Ln=Eu, Gd, Tb) in MeOH resulted in the isolation of [LnL]?HCl complexes characterized by elemental analysis, mass and IR spectroscopy. Photophysical studies of the Eu and Tb complexes in aqueous solutions revealed the characteristic luminescence features of the metal atoms, indicative of an efficient ligand‐to‐metal energy‐transfer process. Determination of the luminescence quantum yields in H₂O showed the Tb complex to be highly luminescent (?=15%), while, for the Eu complex, the quantum efficiency was only 2%. Excited‐state‐lifetime measurements in H₂O and D₂O evidenced the presence of ca. three H₂O molecules in the first coordination sphere of the complexes. Investigation of the Gd complex allowed the determination of the ligand‐centered triplet state and showed the ligand to be well suited for energy transfer to the metal. The luminescence properties of the complexes are described, and the properties of the ligand as a suitable complexation pocket is questioned.     

Tb(III)与PNIPAM接枝核壳纳米微球相互作用的研究

利用透射电镜、X射线光电子能谱、动态激光光散射和荧光光谱技术对Tb(III)与聚N-异丙基丙烯酰胺(PNIPAM)接枝核壳纳米微球PNIPAM-g-P(NIPAM-co-St) (PNNS)的相互作用进行了研究. 结果表明: Tb(III)和热敏性的核壳纳米微球PNNS有显著的相互作用. 其一, Tb(III)可与PNNS中酰胺基团上的氧原子配位形成微球配合物Tb(III)-PNNS; 其二, Tb(III)-PNNS微球配合物兼具热敏性; 其三, 该配合物在545 nm处的荧光强度较Tb(III)增大了233倍, Tb(III)与PNNS分子间能量传递达到50%, 当Tb(III) 质量分数为12%时荧光强度最大.     

含铽三元共聚物的合成及其发光性能研究

报道了新型的可平衡电荷(空穴与电子)传输的稀土铽-聚合物发光材料的合成, 将稀土铽配合物单体与乙烯基咔唑、甲基丙烯酸甲酯共聚制得含咔唑和稀土铽配合物的HTL-EML-ETL三功能合一的聚合物, 通过FT-IR, GPC, NMR及元素分析对其结构进行表征, 并研究了这类材料的光致及电致发光性能. 在含铽三元共聚物的薄膜荧光中, 来自咔唑基的荧光出现“固态猝灭”, 而来自稀土铽离子的荧光则明显加强, 这是由于二者的失活机制不同引起的. 以含铽三元共聚物制作的单层器件主要发射铽离子的特征荧光.     

铽配合物Tb(PMIP)3(PhCA)的合成及阴离子识别研究

本文设计合成了稀土铽配合物Tb(PMW)3(PhCA)作为阴离子试剂,利用荧光光谱考察了其与F-、Cl-、Br-、I-、ClO4-、NO3-、AcO-和H2PO-4等阴离子的作用.研究结果表明:不同阴离子的加入能够调控,Tb(PMIP)3(PhCA)的发光行为,当一定量的氟离子(醋酸根离子、磷酸二氢根离子)加入到Tb(PMIP)3(PhCA)的乙腈溶液中后,荧光发射增强;过量的氟离子(醋酸根离子、磷酸二氢根离子)加入后则使其荧光淬灭.而在乙腈和水混合溶液中,Tb(PMIP)3(PhCA)则能选择性识别氟离子和磷酸二氢根离子.     

水溶液中P(AM-co-PEBA)聚合物对Tb3＋离子荧光增强作用

考察了Tb3＋离子在模板法合成的疏水缔合水溶性聚合物聚丙烯酰胺/4-(ω-丙烯酰氧乙氧基)苯甲酸(P(AM-co-PEBA))溶液中的荧光增强行为. 在溶液中P(AM-co-PEBA)通过羧基的络合作用及疏水缔合作用, 改变了 Tb3＋离子所处微环境, 降低了Tb3＋离子络合水的个数, 提高了Tb3＋离子荧光强度. 聚合物中PEBA含量增加或PEBA以微嵌段结构存在, 这一微环境效应得到增强. 另一方面, 聚合物P(AM-co-PEBA)分子内具有紫外光捕获基团, 可通过“天线效应”与Tb3＋离子进行能量传递, 进一步提高了Tb3＋离子的荧光强度.     

Controlled polymerization of carbazole‐based vinyl and methacrylate monomers at ambient temperature: A comparative study through ATRP,SET, and SET‐RAFT polymerizations

The polymerization of N‐vinylcarbazole (NVK) and carbazole methacrylate (CMA) was carried out using controlled radical polymerization methods such as atom transfer radical polymerization (ATRP), single electron transfer (SET)‐LRP, and single electron transfer initiation followed by reversible addition fragmentation chain transfer (SET‐RAFT). Well‐controlled polymerization with narrow molecular weight distribution (M_w/M_n) < 1.25 was achieved in the case of NVK by high‐temperature ATRP while ambient temperature SET‐RAFT polymerization was relatively slow and controlled. In the case of CMA, SET‐RAFT is found to be more suitable for the ambient temperature polymerization. The polymerization rate followed first order kinetics with respect to monomer conversion and the molecular weight of the polymer increased linearly with conversion. The controlled nature of the polymerization is further demonstrated by the synthesis of diblock copolymers from PNVK and PCMA macroinitiators using a new flavanone‐based methacrylate (FMA) as the second monomer. All the polymers exhibited fluorescence. The excimer bands in the homopolymers of PNVK and PCMA were very broad, which may be attributed to the carbazole–carbazole overlap interaction. The scanning electron microscopy analysis of the block copolymer reveals interesting morphological features. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Photoluminescence property of polymer–rare earth complexes containing acetaldehyde/aminophenol type bidentate Schiff base ligand

Acetaldehyde was introduced onto the side chains of polysulfone, and then Schiff base reactions were carried out between the introduced acetaldehyde and ortho-aminophenol (OAP) or meta-aminophenol (MAP). Two bidentate Schiff base (B) ligands of acetaldehyde/aminophenol type, OAPB and MAPB, were bonded on the side chains of polysulfone, and two new bidentate Schiff base ligand functionalized-polysulfones, PSF-OAPB and PSF-MAPB, were obtained. The triplet state energies of OAPB and MAPB are well matched with the resonant level energy of Tb(III), and the Tb(III) complexes emit the strong characteristic fluorescence of Tb(III) (green luminescence). Complexes of Eu(III) have no fluorescence emission because of the mismatching of the energy levels. In comparison, the fluorescence intensity of the binary complex PSF-(MAPB)₃-Tb(III) is stronger than that of the binary complex PSF-(OAPB)₃-Tb(III) because of the structured difference of the chelating ring. The ternary complexes PSF-(MAPB)₃-Tb(III)-(Phen)₁ (Phen represents 1,10-phenanthroline) and PSF-(OAPB)₃-Tb(III)-(Phen)₁ have stronger fluorescence emissions than the corresponding binary complexes. The fluorescence emission intensities of solid films of the complexes are stronger than that of their solutions. The prepared luminescent polymer-Tb(III) complexes containing acetaldehyde/aminophenol type bidentate Schiff base ligands have very high quantum yields (80–86%), reflecting the high intramolecular energy transfer efficiencies from the ligands to Tb(III).