两个发光铽(Ⅲ)配合物的晶体结构和荧光性质

采用水热法合成了两个稀土配合物[Tb(3-SBA)(IP)OH(H₂O)]·H₂O (1)和[Tb(dpdc)_1.5(IP)(H₂O)]_n(2)(3-SBA=3-羧基苯磺酸根,dpdc=2,2′-联苯二甲酸根,IP=1H-咪唑[4,5-f][1,10]-邻菲啰啉),并用X-ray单晶衍射仪测定了它们的晶体结构。配合物1是由3-羧基苯磺酸根和羟基交替连接Tb(Ⅲ)离子形成的一维链。配合物2是由2,2′-联苯二甲酸根桥联Tb(Ⅲ)离子形成的一维链。配合物1与2在紫外灯下均发出强的绿色荧光,其荧光光谱中有四个发射峰,位于492,544,584和619 nm,分别对应于Tb(Ⅲ)离子的5D₄→7F_J(J=6-3)跃迁,其发射光谱中均不存在配体荧光。配体吸收紫外光,有效地转移能量给Tb(Ⅲ)离子。配合物1与2中Tb(Ⅲ)离子的5D₄发光显示了单指数衰减,寿命分别为0.287和0.439 ms,发光量子产率分别为9.28%和7.07%。     

对氨基马尿酸铽二元、三元配合物的合成、表征及荧光光谱研究

在乙醇溶液中以邻菲咯啉(phen)、2,2’-联吡啶(bipy)和对氨基马尿酸(PAH,HL)为配体与铽离子(Tb(Ⅲ))合成了二元和三元稀土配合物。通过元素分析、差热-热重分析、紫外光谱、红外光谱分析,确定了配合物的组成为TbL₃(1)、TbL₃·phen·H₂O(2)和TbL₃·bipy·H₂O(3),并讨论了配合物1～3的谱学性质和荧光性能。推测出羧基中的氧原子以桥式双齿的形式与稀土离子配位。由红外光谱和热分析测试确定的配合物1及配合物2中的水分子未参与配位。研究表明,铽配合物在489,583和621 nm处出现发射峰,它们分别归属于5D₄→7F₆,5D₄→7F₅,5D₄→7F₄和5D₄→7F₃的跃迁。其中544 nm处5D₄→7F₅跃迁的强度最强,配体的共平面性和共轭性越大,配合物的荧光性能越高,三元配合物TbL₃·phen·H₂O和TbL₃·bipy·H₂O的荧光强度优于二元配合物TbL₃的荧光强度。     

铕、铽-2-噻吩甲酸-2,2′-联吡啶配合物的合成、表征及荧光性质研究

合成了铕、铽-2-噻吩甲酸的二元配合物和铕、铽-2-噻吩甲酸-2,2′-联吡啶的三元配合物,并对它们进行了元素分析、稀土络合滴定、摩尔电导测定,确定了配合物组成分别为REL₃·2H₂O及REL₃ L′·C₂H₅OH(RE=Eu,Tb; L=2-噻吩甲酸、L′=2,2′-联吡啶), 测定了配体及配合物的IR谱、1H NMR谱及荧光光谱。IR谱和1H NMR谱测定表明,配体2-噻吩甲酸羧基氧、配体邻菲咯啉2个氮原子与稀土离子配位。荧光光谱实验表明,高氯酸铕和高氯酸铽分别与2,2′-联吡啶和2-噻吩甲酸反应形成的三元配合物的荧光明显强于二元配合物。     

3-甲基-1-乙酰基-5-(2-羟基苯基)-4,5-二氢吡唑及其铕和铽配合物的合成与光谱学研究

以六水合硝酸铽和六水合硝酸铕,3-甲基-1-乙酰基-5-(2-羟基苯基)-4,5-二氢吡唑(HL),1,10-邻菲罗啉和三苯基氧磷(TPPO)合成了TbL₃·2H₂O,TbL₂(phen)·H₂O,TbL₂(TPPO),EuL₃·2H₂O,EuL₂(phen)·2H₂O,EuL₂(TPPO)·2H2O 6个固体配合物。用元素分析,红外光谱,荧光光谱对配合物进行了组分确定和结构表征。IR表明,自由配体HL与稀土离子配位后,位于1644 cm-1处的ν_CC发生移动,相应的ν_CN振动吸收峰降到了1 600 cm-1,结合元素分析等其他表征说明HL和稀土离子发生配位。室温下测定了配合物的荧光激发光谱和发射光谱,激发光谱表明配合物EuL₂(Phen)·2H₂O和TbL₂(Phen)·H₂O的最佳激发波长分别为310和320 nm, 在此激发波长下扫描发射光谱,EuL₂(Phen)·2H₂O和TbL₂(Phen)·H₂O相对荧光强度最强,第二配体phen对Eu3+和Tb3+离子的荧光发射强度有明显的增强作用。     

3,4-噻吩二羧酸、1,10-邻菲罗啉与稀土配合物的荧光性质及对硝基苯的检测

3,4-噻吩二羧酸(3,4-H₂tdc),1,10-邻菲罗啉(phen)和稀土硝酸盐经水热法合成三种配合物Ln₂(Htdc)₂(tdc)₂(phen)₂(H₂O)₄(Ln=Eu 1, Gd 2, Tb 3),并用X-射线单晶衍射分析方法测定了配合物1-3晶体结构,配合物1-3为双核分子。每个金属离子周围有2个3,4-tdc,1个3,4-Htdc,1个phen和2个配位水分子,配位数为9。配合物1和3在紫外灯下显强红光和绿光,其荧光发射光谱,在619和545 nm出现最大发射峰,分别对应于Eu(Ⅲ)离子的5D₀→7F₂和Tb(Ⅲ)离子的5D₄→7F₅跃迁。配合物2在425 nm观察到来自基于配体的π*→π最大发射峰。不同溶剂分子对配合物1荧光有不同程度的影响,基于荧光猝灭机理,配合物1具有选择性检测硝基苯污染物的能力。     

稀土配合物掺杂凝胶的原位光声光谱研究及其共发光效应

采用溶胶-凝胶方法,制备了Ln(Sal)₃·H₂O(Ln3+∶La3+, Nd3+, Tb3+; Sal: 水杨酸) 稀土配合物掺杂的二氧化硅凝胶样品。首次采用光声光谱对稀土配合物在凝胶中的形成进行研究。结果表明,经110 ℃热处理后,Tb3+, La3+和Nd3+配合物掺杂的凝胶样品在配体吸收处的光声强度依次明显增强;而对仅在室温陈化、干燥的湿凝胶样品,其配体吸收处的光声强度几乎完全相同。研究发现,未经适当的热处理过程凝胶样品中稀土配合物尚不能形成。结合荧光光谱,分析了凝胶中稀土离子配位环境的变化和稀土配合物的形成。首次发现了稀土芳香羧酸配合物掺杂凝胶的共发光效应,考察Tb_0.8Gd_0.2(Sal)₃·H₂O和Tb_0.8Nd_0.2(Sal)₃·H₂O配合物掺杂的凝胶样品,发现Gd3+离子的引入了增强了凝胶样品中Tb3+的发光效率,而Nd3+离子的引入明显减弱了凝胶中Tb3+的发光,并对共发光效应可能的机理进行了讨论。     

卤代苯甲酸铽与1, 10-邻菲哕啉三元配合物的合成及性质

以卤代苯甲酸和1,10-邻菲哕啉为配体,合成了9种Tb(Ⅲ)的三元配合物,以EDTA配位滴定分析和元素分析确定了各配合物的组成。通过红外光谱分析对配合物的结构进行了初步表征,在配合物中羧基氧原子和1,10-邻菲啰啉中的氮原子均参与了配位。采用TG-DTG技术对配合物的热稳定性进行了研究,9种配合物均有较好的热稳定性,它们的热稳定性顺序为:Tb(o-ClBA)₃phen>Tb(o-BrBA)₃phen>Tb(p-ClBA)₃phen>Tb(m-BrBA)₃phen·H₂O>Tb(o-FBA)₃phen>Tb(p-BrBA)₃phen>Tb(p-FBA)₃phen>Tb(m-ClBA)₃phen≈Tb(m-FBA)₃phen·H₂O。在同一条件下测得了各配合物固体粉末的激发和发射光谱,结果表明:相同取代基和相同取代位置的各组配合物的两个较强发射峰(⁵D₄-⁷F₆和⁵D₄-⁷F₅)的荧光强度顺序分别为:Tb(o-FBA)₃phen>Tb(p-FBA)₃phen>Tb(m-FBA)₃phen·H₂O,Tb(m-ClBA)₃phen>Tb(p-ClBA)₃phen>Tb (o-ClBA)₃phen,Tb(p-BrBA)₃phen>Tb(o-BrBA)₃phen>Tb(m-BrBA)₃phen·H₂O和Tb(o-FBA)₃phen>Tb (o-BrBA)₃phen>Tb(o-ClBA)₃phen,Tb(m-ClBA)₃phen>Tb(m-FBA)₃phen·H₂O>Tb(m-BrBA)₃phen·H₂O,Tb(p-BrBA)₃phen>Tb(p-ClBA)₃phen>Tb(p-FBA)₃phen[其中o(m,p)-F(Cl,Br)BA为邻(间,对)氟(氯,溴)苯甲酸根,phen为1,10-邻菲哕啉]。     

铽配合物与PVK混合体系的发光研究

研究了铽配合物[Tb(m-MBA)₃phen]₂·2H₂O与PVK共掺杂体系的激发光谱和光致发光谱, 发现两者之间存在着能量转移,由于PVK的发射光谱和铽配合物的激发光谱重叠很小,两者之间发生Frester能量传递的几率很小,铽的发光主要是由于铽配合物的配体俘获了电子-空穴对使配体受到激发而导致的,在电致发光中, PVK的发光完全被抑制, 与光致发光的表现不同, 这是由于两种发光(光致和电致)机理不同造成的。     

低温固相反应合成苯乙酸稀土配合物及铕(Ⅲ)、铽(Ⅲ)的发光性能

采用低温固相反应合成了4种苯乙酸稀土配合物:RE(L)3.nH2O(n=0.5～1.5;RE=La,Nd,Eu,Tb;L=C6H5CH2COO-),经元素分析、稀土络合滴定、摩尔电导及热重分析确定了配合物的组成,测定了配体及配合物的IR谱、1HNMR及配体的磷光光谱和铕、铽配合物荧光激发和发射光谱。根据磷光发射光谱数据计算了配体的三重态平均能级值。铕(Ⅲ)、铽(Ⅲ)配合物的荧光光谱和配体的磷光光谱表明,配体仅对铽(Ⅲ)的荧光具有一定的敏化作用。对镧配合物进行了扫描电镜形貌分析,发现苯乙酸镧为球状空穴结构,粒径在十几微米到几十微米。     

均苯三甲酸Eu-Tb配合物的合成及荧光性质研究

以H₃BTC为配体,用水热法合成了均苯三甲酸Eu-Tb系列发光配合物Eu_1-xTb_x BTC·nH₂O(H₃BTC=1,3,5-均苯三甲酸,x=0,0.1,0.3,0.5,0.7,0.9,1.0;n=0, 0.5),通过化学分析及元素分析确定了配合物的组成,用红外光谱对其进行了表征;研究了配合物的激发光谱和发射光谱,并就其荧光强度与两种稀土离子含量之间的关系进行了讨论。结果表明：(1)该系列配合物(除纯均苯三甲酸Tb外)均发出Eu离子的特征荧光,而荧光强度随着Eu和Tb离子的不同发生了明显变化,发射峰位置基本不变;(2)系列配合物中Tb对Eu的荧光强度有敏化作用,Eu对Tb的荧光强度有猝灭作用;同时Eu离子的5D₀→7F₁和5D₀→7F₂跃迁发射强度较强,且均劈裂为两个峰(587,593 nm)及(611.2,618 nm),这是由于Eu离子所处的配位环境不同所引起的。     

铕、铽-2-噻吩甲酸-2,2''''-联吡啶配合物的合成、表征及荧光性质研究

合成了铕、铽-2-噻吩甲酸的二元配合物和铕、铽-2-噻吩甲酸-2,2'-联吡啶的三元配合物,并对它们进行了元素分析、稀土络合滴定、摩尔电导测定,确定了配合物组成分别为REL3·2H2O及REL3 L'·C2H5OH(RE=Eu,Tb;L=2-噻吩甲酸、L'=2,2'-联吡啶),测定了配体及配合物的IR谱、1H NMR谱及荧光光谱.IR谱和1H NMR谱测定表明,配体2-噻吩甲酸羧基氧、配体邻菲咯啉2个氮原子与稀土离子配位.荧光光谱实验表明,高氯酸铕和高氯酸铽分别与2,2'-联吡啶和2-噻吩甲酸反应形成的三元配合物的荧光明显强于二元配合物.     

在铕-2-噻吩甲酸-邻菲咯啉三元配合物中La3+对Eu3+的发光影响

合成了七种不同掺杂比例的稀土高氯酸盐(铕掺镧)与2-噻吩甲酸-邻菲咯啉的固态配合物,对配合物进行了元素分析、稀土络合滴定、摩尔电导测定,确定了配合物组成为(Eu1-xLax)·L3·phen·1/2H2O(x=0·000～0·200,L为2-噻吩甲酸,phen为邻菲咯啉),并测定了配体及配合物的IR谱及荧光激发和发射光谱。摩尔电导数据表明,此类配合物为非电解质。红外光谱测定表明,配体2-噻吩甲酸羧基氧与稀土离子配位,配体1,10-邻菲咯啉两个氮原子与稀土离子配位。荧光光谱测定表明,Eu3 处于无反演对称中心格位上,Eu3 配合物发射强度增大。配合物中La3 对Eu3 的发光产生敏化增强效应,当La3 掺入量为0·005mol时敏化强度最大,随着La3 浓度的增大,对Eu3 的发光敏化强度降低。     

Enhanced fluorescence of Tb(III), Dy(III) perchlorate by salicylic acid in bis(benzoylmethyl) sulfoxide complexes and luminescence mechanism

Two novel ternary rare earth perchlorate complexes had been synthesized by using bis(benzoylmethyl) sulfoxide as first ligand (L=C₆H₅COCH₂SOCH₂COC₆H₅), salicylic acid as second ligand (L^′=C₆H₄OHCOO⁻). The compounds were characterized by elemental analysis, TG-DSC and molar conductivities in DMF solution. The composition was suggested as [REL₅L′](ClO₄)₂·nH₂O (RE=Tb, Dy; n=6, 8 ). Based on IR, ¹HNMR and UV spectra, it showed that the first ligand, bis(benzoylmethyl) sulfoxide (L), bonded with Tb(III), Dy(III) ions by the oxygen atom of sulfinyl group. The second ligand, salicylic acid group (L′), not only bonded with RE(III) ions by one oxygen atom of carboxyl group but also bonded with RE(III) ions by oxygen atom of phenolic hydroxyl group. In bis(benzoylmethyl) sulfoxide system, fluorescent spectra of the complexes showed that the luminescence of Tb(III), Dy(III) ions was enhanced by the second ligand salicylic acid. The ternary complexes had stronger fluorescence than the binary ones where only bis(benzoylmethyl) sulfoxide acted as ligand. Phosphorescent spectra of the two ligands indicated that the coordination of salicylic acid resulted in the matching extent increasing between the triplet state of ligand and excited state of the rare earths. The relationship between fluorescence lifetime and fluorescence intensity was also discussed.     

对氯苯甲酸-2,4,6-三吡啶基三嗪稀土配合物的合成、表征及发光性能

以对氯苯甲酸为第一配体,2,4,6-三吡啶基三嗪(TPTZ)为第二配体,分别以铕、铽和镝为中心,合成了10种稀土配合物,并进行了元素分析、稀土络合滴定、等离子光谱、紫外光谱、红外光谱和发光光谱测定。配合物的组成为:RE(p-ClBA)3(TPTZ).2H2O和RE0.5Ln0.5(p-ClBA)3(TPTZ).2H2O(RE=Eu3+,Tb3,+Dy3+;Ln=La3,+Gd3,+Y3;+p-ClBA=对氯苯甲酸根;TPTZ=2,4,6-三吡啶基三嗪),均为非电解质;对氯苯甲酸的羧基氧原子与稀土离子配位,2,4,6-三吡啶基三嗪以主配位点上的3个氮原子与稀土离子配位;铕配合物的发光强度大于铽配合物的,镝配合物发光最弱;在上述3种发光稀土配合物中分别掺入发光惰性稀土离子镧、钆及钇后,发光强度有不同改变,掺入镧可明显增强铕、铽的发光强度,钆可敏化铕、铽和镝的发光,而钇的敏化作用较弱。表明:掺杂配合物并不完全是两种简单配合物的机械混合,而是有混配配合物生成。     

铽掺钇配合物[(TbxY1-x)(HL)L'Cl·1/2H2O]的合成及荧光性质研究

以1,3,5-苯三甲酸根(BTC3-)为阴离子配体,1,10邻菲啰啉(phen)为中性配体,以不同摩尔比铽、钇离子为中心体,合成了系列铽掺钇配合物.经C,N,H元素分析,稀土总量络合滴定和铽、钇分量的测定推测配合物的组成为(TbxY1-x)(HL)L'C1·1/2H2O(x=0.10,0.30,0.50,0.70,0....     

Spectroscopic studies of lanthanide(III) ion complexes with diethyl(phthalimidomethyl) phosphonate

Complexation and photophysical properties of complexes of lanthanide ions, Ln(III), with diethyl(phthalimidomethyl)phosphonate ligand, DPIP, were studied. Interactions between Ln(III) and DPIP were investigated using Nd(III) absorption and Eu(III) and Tb(III) luminescence (emission and excitation) spectra, recorded in acetonitrile solution containing different counter ions (NO₃^-, Cl^- and ClO₄^-). Results of the absorption spectroscopy have shown that counter ions play a significant role in the complexation of Ln(III)/DPIP complexes. Studies of luminescence spectra of Eu(III) and Tb(III) ions proved that the formation of Ln(III)/DPIP complexes of stoichiometry Ln:L=1:3 is preferred in solution. Based on the results of elemental analysis, Nd(III) absorption spectra and IR and NMR data, it was shown that the DPIP ligand binds Ln(III) ions via oxygen from phosphoryl group, forming complexes of a general formula Ln(DPIP)₃(NO₃)₃·H₂O, in which the NO₃^- ions are coordinated with the metal ion as bidentate ligands. Luminescent properties and energy transfer, from the ligand to Ln(III) ions in the complexes formed, were studied based on the emission and excitation spectra of Eu(III) and Tb(III). Their luminescent lifetimes and emission quantum yields were also measured.     

Synthesis,characterization, luminescence properties and antioxidant activity of Ln(III) complexes with a new aryl amide bridging ligand

A novel Aryl amide ligand H₂L and its eight complexes, [LnH₂L(NO₃)₂·H₂O]NO₃ [Ln=Sm(III), Er(III), Tb(III), Dy(III), La(III), Gd(III), Nd(III), and Pr(III)], are presented. The ligand and complexes were synthesized and characterized based on elemental analyses, molar conductance, IR, ¹H and ¹³C-NMR, UV–VIS., and TGA studies. The conductivity data show a 1:1 electrolytic nature with a general formula [LnH₂L(NO₃)₂·2H₂O]NO₃ The IR spectra reveal coordination of the ligand through the azomethine nitrogen and the phenolic hydroxyl of the ligand to the lanthanide ion. The coordinated nitrate ions behave in a bidentate fashion. The thermal decomposition studies indicate the presence of two water molecules in the inner coordination sphere. Under the excitation at 319 nm, the luminescence emission properties for Sm, Tb, and Dy complexes are observed. These observations show that the ligand favors energy transfers to the emitting energy level of these lanthanide ions. Furthermore, the antioxidant activity of the ligand and its Ln(III) complexes was determined by DPPH radical scavenging method, which indicates that the Ln(III) complexes exhibit more effective antioxidant activity than the ligand alone.     

Preparation, Characterization and Photophysical Properties of Highly Luminescent Terbium Complexes Incorporated Into SiO2/Polymer Hybrid Material

Two new highly luminescent Tb(III) coordination complexes of beta-diketone ligands, [TbL(capital I, Ukrainian)(NO(3))(3)(H(2)O)] 1 [L(capital I, Ukrainian)=N-(2-pyridinyl)ketoacetamide] and [TbL(capital I, Ukrainiancapital I, Ukrainian) (2)(NO(3))(2)(C(3)H(6)O)][TbL(capital I, Ukrainiancapital I, Ukrainian)(NO(3))(4)] 2 [L(capital I, Ukrainiancapital I, Ukrainian)=N-(6-(4-methylpyridinyl))ketoacetamide], were synthesized and characterized by single crystal X-ray diffraction, and incorporated into SiO(2)/polymer hybrid material by sol-gel method resulting in a novel ternary molecular hybrid material. The Tb(III) complexes display characteristic metal-centered luminescence while the ligands emission are completely quenched, showing that efficient ligand-to-metal energy transfer (antenna effect) occurs. The gels can exhibit the characteristic emission bands of terbium ion. In addition, terbium ions present longer fluorescence lifetime in gels than in the corresponding pure complexes powders. Compared with the complexes, the unit mass luminescence intensities of the gels are enhanced. And the increase extent of luminescence intensity of the gel is influenced by the substituent of the ligands. At the same time, concentration effects on the luminescence intensity were investigated. The photo stabilities of the gels under UV radiation are much better than those of the pure terbium complexes.     

苯甲酸及其衍生物与1,10-邻菲咯啉铽的三元配合物的荧光光谱研究

分别以苯甲酸及邻、间、对甲基(甲氧基)苯甲酸为第一配体, 以邻菲咯啉(phen)为第二配体, 合成了七种Tb(Ⅲ)的三元配合物. 通过元素分析确定了各配合物的组成. 在室温下, 测定了各固体配合物的激发和发射光谱, 讨论了不同种类、不同位置的取代苯甲酸作第一配体对铽三元配合物荧光性质的影响. 结果表明, 取代苯甲酸作第一配体的Tb(Ⅲ)三元配合物的最佳发射峰5D4→7F6(489 nm), 5D4→7F5(545 nm)的强度, 均比苯甲酸作配体的配合物强. 甲基为取代基的苯甲酸的三种配合物中, 最佳发射峰的强度顺序为: Tb(o-MBA)3phen ＜Tb(m-MBA)3phen*H2O＜Tb(p-MBA)3phen(其中o-MBA为邻甲基苯甲酸根、 m-MBA为间甲基苯甲酸根、 p-MBA为对甲基苯甲酸根、 phen为邻菲咯啉);甲氧基为取代基的苯甲酸的三种配合物中, 最佳发射峰强度顺序为: Tb(o-MOBA)3phen·H2O＞ Tb(m-MOBA)3phen·H2O ＞Tb(p-MOBA)3phen(其中o-MOBA为邻甲氧基苯甲酸根、 m-MOBA为间甲氧基苯甲酸根、 p-MOBA为对甲氧基苯甲酸根).