芳香羧酸铕-含氮杂环配体三元配合物的合成及性质研究

分别以苯甲酸、苯乙酸、β-苯丙酸、苯丙烯酸为第一配体,1,10-邻菲口罗啉或2,2′-联吡啶为第二配体,合成了7种铕(Ⅲ)的三元配合物。通过元素分析、配位滴定分析,确定了各配合物的组成。通过红外光谱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邻菲口罗啉及联吡啶中的氮原子均参与了配位。采用TG-DTG技术对7种配合物的热分解过程进行了研究,以phen为第二配体的4种铕(Ⅲ)的三元配合物具有良好的热稳定性。室温下测定了各配合物粉末的激发和发射光谱。结果表明:羧酸配体相同,以邻菲口罗啉为第二配体的配合物的荧光强度要大于以联吡啶为第二配体的配合物的相应荧光强度。7种铕(Ⅲ)的三元配合物中,最强发射峰强度顺序为:Eu(-βPPA)3phen>Eu(BA)3phen>Eu(PLA)3phen>Eu(BA)3bipy>Eu(PLA)3bipy>Eu(CA)3phen.H2O>Eu(CA)3bipy(其中BA为苯甲酸根、PLA为苯乙酸根、β-PPA为β-苯丙酸根、CA为苯丙烯酸根、phen为1,10-邻菲口罗啉、bipy为2,2′-联吡啶)。     

新的稀土Eu,Tb(Ⅲ)β-二酮三元配合物的合成与光谱性质

采用Claisen缩合反应合成了一种β-二酮1-(4-氨基苯)-3-苯基丙烷-1,3-二酮(L:C15H13NO2),以元素分析和1H NMR谱确定了其组成,核磁和红外分析结果表明L主要以烯醇式存在。以L为第一配体,分别以邻菲罗啉(phen),2,2’-联吡啶(bipy)为第二配体,合成了新的稀土Eu,Tb(Ⅲ)三元配合物。通过元素分析、红外光谱、紫外光谱、磷光光谱和荧光光谱对合成的配合物进行了表征。荧光光谱表明:稀土铽配合物的发光性能优于稀土铕配合物,进一步研究表明配体L与Tb3+间能级差较匹配,分子内传能效率高;phen对配合物的荧光敏化效果优于bipy,表明第二配体的刚性和共轭性越大,配合物的发光性能越好。     

β-二酮(HTPP)、邻菲罗啉分别与铕和铽三元配合物的合成、 荧光性能及理论研究

合成了一个新的β-二酮配体1-(2-噻吩基)-3-(对苯乙炔基苯基)-1,3-丙二酮(HTPP), 并用HTPP、邻菲罗啉(phen) 分别与Eu(III)和Tb(III)反应, 生成了两个新的三元稀土配合物Eu(TPP)3phen和Tb(TPP)3phen, 用红外光谱、化学分析、元素分析及热重分析对它们的组成和结构进行了表征. 室温下, 在紫外光激发下Eu(III)和Tb(III)的配合物表现出中心离子的特征荧光发射, 发现β-二酮配体对配合物的荧光有较大影响, 通过量子化学计算从理论上对实验结果进行了解释.     

新型稀土Eu,Tb(Ⅲ)芳香羧酸配合物的合成及发光性能

以2-二苯胺羰基苯甲酸(L)为第一配体,咪唑并[5,6-f]邻菲罗啉(IP)为第二配体,合成出新型稀土铕、铽三元配合物。采用元素分析、红外光谱、紫外-可见光谱对配体和配合物的结构进行了表征。红外光谱分析表明配合物中的稀土离子与第一配体L中的氧原子以及第二配体IP中的氮原子进行了配位。紫外光谱表明配合物主要是由第一配体L吸收能量。通过荧光光谱、荧光量子效率和荧光寿命研究了配合物的荧光性能,结果显示:两种配合物均表现出稀土离子的特征发射,且配合物的荧光量子效率和荧光寿命与发光强度成正比,配合物Tb(L)3IP的各项荧光性能均优于Eu(L)3IP。     

钐、铕-2,4-二氯苯氧乙酸的二元、三元配合物的合成及荧光性能

以2,4-二氯苯氧乙酸为第一配体、1,10-菲罗啉为第二配体,合成了钐、铕的二元、三元配合物。通过元素分析、EDTA络合滴定及热重分析,确定了配合物的通式为RE(DCP)3.H2O,RE(DCP)3phen(RE=Sm,Eu;DCP=2,4-二氯苯氧乙酸根;phen=邻菲罗啉);测定了配合物红外光谱、紫外光谱、荧光光谱;研究了配合物的热稳定性。结果表明,三元配合物较二元配合物稳定;Eu(DCP)3.H2O和Eu(DCP)3phen具有荧光性能。     

一个新型钌(Ⅱ)配合物对F~-的双重光谱识别

采用紫外-可见光谱和荧光光谱滴定方法研究了钌(Ⅱ)配合物[Ru(bpy)(H2iip)2](ClO4)2[bpy=2,2'-联吡啶,H2iip=2-吲哚基-咪唑并[4,5-f][1,10]-邻菲罗啉]在DMSO溶液中对卤素离子的识别性质.结果表明该配合物能比色和荧光双重光谱高选择性识别F-.     

一个新型钌(II)配合物对F－的双重光谱识别

采用紫外-可见光谱和荧光光谱滴定方法研究了钌(II)配合物[Ru(bpy)(H2iip)2](ClO4)2 [bpy＝2,2’-联吡啶, H2iip＝2-吲哚基-咪唑并[4,5-f][1,10]-邻菲罗啉]在DMSO溶液中对卤素离子的识别性质. 结果表明该配合物能比色和荧光双重光谱高选择性识别F－.     

铽配合物Tb(2-MBA)_3·2H_2O和Tb(2-MBA)_3 phen的荧光性能研究

以2-甲基苯甲酸(2-MBA)为第一配体、1,10-邻菲罗啉(phen)为第二配体,制备了三元铽配合物Tb(2-MBA)3phen和二元铽配合物Tb(2-MBA)3·2H2O,并利用元素分析、红外光谱、紫外光谱、荧光光谱和荧光寿命对二者的结构与性能进行分析表征。研究结果表明:三元铽配合物Tb(2-MBA)3phen的荧光发射强度要强于二元铽配合物Tb(2-MBA)3·2H2O,而二者的荧光寿命恰好相反,三元铽配合物Tb(2-MBA)3phen的荧光寿命短于二元铽配合物Tb(2-MBA)3·2H2O。热重分析表明Tb(2-MBA)3·2H2O的热分解温度要远高于Tb(2-MBA)3phen。     

Eu(DMBM)2(2,2′-bipy)NO3的合成与荧光光谱

本工作首次合成了Eu(DMBM)₂(2,2′-bipy)NO₃(DMBM=二对甲氧基苯甲酰甲烷,2,2′-bipy-2,2′-联吡啶)。通过元素分析、热谱、电导率、红外和拉曼光谱、质子核磁共振谱对所合成化合物进行了表征。在77K测定了固体配合物的激发光谱和发光光谱。光谱数据说明配合物含有两种Eu(Ⅲ)格位。配合物中三种配体在Eu(Ⅲ)周围的分布情况略有不同,显示出不同的晶体场效应。光谱数据表明,配合物中Eu(Ⅲ)格位属于非中心对称的点群C₁或C₃或C₂。     

β-二酮、邻菲罗啉分别与铕和铽三元配合物的合成及发光性能研究

为了寻找新的发光材料并研究β-二酮对稀土配合物发光性能的影响, 我们合成了一个新的β-二酮配体: 1-苯 基-3-(对苯乙炔苯基)-1,3-丙二酮(HPPP), 并用HPPP、邻菲罗啉(phen)分别与Eu(III)和Tb(III)反应, 合成了两个新的三元稀土配合物: Eu(PPP)3phen和Tb(PPP)3phen, 通过红外光谱、化学分析、元素分析对三元稀土配合物的组成和结构进行了表征. 研究了配合物的荧光性质, 发现β-二酮配体对配合物的发光有较大影响, 通过量子化学计算对实验结果进行了解释.     

苯甲酰水杨酸的制备及其与稀土络合物光致发光现象研究

合成了苯甲酰水杨酸,以之为第一配体,以邻菲罗啉（phen)为第二配体,合成了Eu^3 的三元络合物以及Tb^3 的二元络合物。红外光谱说明苯甲酰水杨酸与稀土离子形成了络合物;荧光光谱显示铕络合物具有很好的单色性,并探讨了加入PVK后络合物对称性的变化。     

The study on the effect and mechanism of the second ligands on the luminescence properties of terbium complexes

The binary complex of Tb(III) with N-phenylanthranilic acid (N-HPA) was synthesized, and the ternary complexes were synthesized by introducing 1,10-phenanthroline (Phen), 2,2'-dipyridyl (Bipy), trioctylphosphine oxide (TPPO) as the second ligand, respectively. These complexes were characterized by infrared spectra, UV spectra and fluorescence spectra. The effect and mechanism of different second ligands on the fluorescent intensity of the terbium N-phenylanthranilic acid complexes was discussed. It showed that all the complexes exhibited ligand-sensitized green emission. The luminescence intensity increased in the sequence of Tb(N-PA)(3)Phen相似文献   

4-卤代苯甲酸铽配合物荧光性能的研究

以4-氯苯甲酸(4-ClBA)、4-溴苯甲酸(4-BrBA)和4-碘苯甲酸(4-IBA)为配体合成了三种4-卤代苯甲酸铽的稀土配合物Tb(4-ClBA)3,Tb(4-BrBA)3和Tb(4-IBA)3,紫外可见光吸收光谱表明,相同摩尔浓度的Tb(4-IBA)3的紫外吸收最强,Tb(4-BrBA)3的紫外吸收强度次之,Tb(4-ClBA)3的紫外吸收最弱,而荧光发射光谱表明,Tb(4-IBA)3和Tb(4-BrBA)3的荧光发射强度远小于Tb(4-ClBA)3的.从配体的结构及配体能级、稀土离子Tb3+能级、配体到稀土离子之间的能量传递等角度对该试验结果进行了分析探讨,结果表明苯甲酸对位的碘原子、溴原子和氯原子与苯环上的碳原子所形成的碳卤键热振动的不同是造成三种稀土配合物荧光强度差别较大的本质原因.     

Influence of anionic functions on the coordination and photophysical properties of lanthanide(III) complexes with tridentate bipyridines

A series of four ligands based on a 5'-methyl-2,2'-bipyridyl framework substituted in the 6 position by a carboxylic acid, a phosphonic acid, a monoethyl ester phosphonic acid, or a diethyl ester phosphonic acid are described. The pK(a) values of all ligands and their assignments are determined by a combination of UV-vis absorption spectroscopy and (1)H and (31)P NMR spectroscopy. The ability of the tridentate ligands to form complexes with trivalent lanthanide cations (Ln = La, Nd, Eu, and Lu) in buffered water solutions (Tris-HCl, pH = 7.4) is studied by UV-vis absorption spectroscopy and (1)H NMR. While the two ester ligands display a weak coordination ability toward lanthanide cations, the acid ligands form stable complexes with 1:1, 1:2, and 1:3 Ln/L ratios. A weak selectivity is observed for the middle of the lanthanide series, and the complexes of the phosphonic acid derivative are up to 2 orders of magnitude more stable than those of the carboxylic acid ligand. Photophysical properties of the free phosphonic and carboxylic acid ligands and of their complexes with La, Eu, Gd, Tb, and Lu are investigated in buffered aqueous solutions both at room temperature and 77 K. An efficient ligand-to-metal energy transfer is observed for both the Eu and Tb complexes. Despite a relatively large energy gap between the ligand-centered (3)pipi* and the Eu((5)D(0)) or Tb((5)D(4)) emitting states, the metal-centered luminescence is well sensitized with quantum yields reaching up to 45.5 and 42.2% for the Tb 1:3 complexes with carboxylic and phosphonic acid ligands, respectively.     

Synthesis, luminescence properties and energy transfer of binary and ternary rare earth complexes with aromatic acids and 1,10-phenanthroline

A series of binary and ternary rare earth (Gd, Eu, Tb) complexes with ortho hydroxyl benzoic acid, para aminobenzoic acid, nicotinic acid and 1,10-phenanthroline were synthesized. Phosphorescence spectra and lifetimes of Gd complexes were measured and the lowest triplet state energies of gadolinium binary complexes and the intramolecular energy transfer efficiencies were determined. The luminescence properties and energy transfer process of Eu3+and Tb3+ complexes were discussed.     

Luminescent lanthanide complexes of a bis-bipyridine-phosphine-oxide ligand as tools for anion detection

The Gd(3+), Tb(3+), and Eu(3+) complexes of a bis-bipyridine-phenylphosphine oxide ligand PhP(O)(bipy)(2) 1 (bipy for 6-methylene-6'-methyl-2,2'-bipyridine) have been synthesized. In acetonitrile solutions at room temperature, the Tb(3+) and Eu(3+) complexes show a metal-centered luminescence, indicative of an efficient energy transfer from the two bipy subunits to the Ln center. The photophysical properties drastically depend on the nature of the anions present in solution. In particular, addition of 2 equiv of nitrate anions to a solution containing the [Ln.1](OTf-)(3) leads to an 11-fold increase of the luminescence intensity for the Eu(3+) and a 7-fold increase for the Tb(3+) complexes. Similar effects are provided with Cl-, F-, and CH(3)COO- anions. UV-vis titration experiments were used to determine association constants for binding of, respectively, one, two, and three anions. Stepwise anion addition has also been investigated on the molecular level using quantum mechanical (QM) calculations for the Eu complexes. These calculations reproduce the experimental findings, especially if solvent molecule addition is taken into account. The X-ray crystal structure of the nitrate salt of the Tb complex, as well as QM calculation of a similar Eu complex, demonstrates the coordination of three nitrate anions in a bidentate mode and the step-by-step relegation of the bipy subunits in the second coordination sphere. These features give valuable insights into the mechanism of the overall light amplification process.     

Development of micromarkers with various photoluminescence colors as tracers for shadowing pursuits.

Micromarkers with five photoluminescence colors were developed as tracers for shadowing pursuits. The markers are colorless powders with particle diameters of several tens to several hundreds of micrometers, prepared using a cryogenic sample crusher. They were visualized using red, green, yellow, magenta or cyan photoluminescence under ultraviolet light at approximately 365 nm. The markers were composed of photoluminescent compounds dispersed in polyvinyl butyral. The photoluminescent compounds in the polyvinyl butyral were stable under ambient conditions for more than one year after application. The compounds with the red, green, yellow, magenta and cyan photoluminescence contained a europium (Eu(3+)) complex, a terbium (Tb(3+)) complex, a mixture of Tb(3+) and Eu(3+) complexes, a mixture of Eu(3+) complex and o-coumaric acid, and a mixture of Tb(3+) complex and 7-hydroxycoumarin along with a few drops of a sodium bicarbonate aqueous solution, respectively. Neodymium (Nd(3+)) and ytterbium (Yb(3+)) complexes with photoluminescence in the near-IR wavelength region can also be added to these visible photoluminescent compounds as secret markers for discrimination. The markers were non-destructively identified using a microscopic FT-IR spectrometer and a microscopic spectrometer equipped with a fluorescence detector.     

4-[(1,3-二氧代丁基)氨基]苯甲酸稀土配合物的合成、表征及发光性质

在乙醇体系中,由主配体4-[(1,3-二氧代丁基)氨基]苯甲酸(H2L,C11H11NO4)、稀土硝酸盐及辅助配体邻菲啰啉(phen)反应合成了两个系列8个配合物[Ln2(L)3(H2O)4]n(Ln=Sm(1),Eu(2),Tb(3),Dy(4));[Ln2(NO3)2(L)2(phen)2]n(Ln=Sm(5),Eu(6),Tb(7),Dy(8))。用元素分析、红外光谱、摩尔电导、热重分析进行表征,确定了产物的化学组成,推断了相应的结构。测定了室温时固体产物的激发和发射光谱,结果表明:由主辅配体共同配位的三元配合物的发光强度好于无辅助配体参与的二元配合物。测定了三元配合物的荧光寿命,其中铕和铽配合物显示较长的荧光寿命。