Synthesis, Characterization and Fluorescence of Terbium(Ⅲ) Complexes with Phenylglyoxylic Acid and 2,2-Dipyridine, 1,10-Phenanthroline, Triphenyl Phosphine Oxide

Three new complexes TbL3dipy （H2O）2, TbL3phen （H2O） 2 and TbL2 （TPPO） 2NO3 were synthesized （L = phenylglyoxylate ion, dipy = 2, 2-dipyridine, phen = 1,10-phenanthmline, TPPO = Triphenyl phosphine oxide）. Elemental analysis, conductivity, IR spectra, and ^1HNMR spectra studies were performed. IR spectra indicate that the carboxylate ion of phenylglyoxylate is coordinated to the Tb（Ⅲ） ion as an unidentate ligand. In ^1HNMR, the signals of different hydrogens in phenylglyoxylate ion shift upfield. The excitation and emission spectra of the three solid complexes were recorded at morn temperature, in which the optimum excitation wavelengths are, 361.0, 359.0 and 367.0 nm for these three complexes, respectively. Four emission bands due to the ^5D4-^7Fj（j = 6, 5, 4, 3） transitions were observed for TbL3dipy（H2O）2（489.0, 545.0, 584.0, 620.0 nm） and TbL3phen（H2O）2（490.0, 544.0, 583.0, 620.0 nm）. Under the same conditions, only one emission band due to the ^5D4-^7F5 transition was observed for the complex TbL2（TPPO）2NO3. The emission intensity of TbL3dipy（H2O）2 is the strongest among the three complexes.

Synthesis, Characterization and Fluorescence Studies on Complexes of Terbium with Phenylglyoxylic Acid, 2,2-Dipyridine, 1,10-Phenanthroline, Triphenyl Phosphine Oxide

Three new complexes TbL3dipy （H2O）2, TbL3phen （ H2O ）2 and TbL2 （ TPPO ）2NO3 have been synthesized （L = phenylglyoxylate ion, dipy = 2, 2- dipyfidine, phen = 1,10-phenanthroline, TPPO = Triphenyl phosphine oxide ）. Elemental analysis, conductivity, IR spectra and ^1HNMR spectra studies were performed on them. IR spectra indicate that carboxylate ions in the phenylglyoxylate are coordinated to Tb （Ⅲ） ions as unidentate ligands. In ^1HNMR, the signals of hydrogens in phenylglyoxylate shift upfield. The excitation and emission spectra of the three comolexes were recorded at room temoerature, the excitation spectra show that the optimum excitation wavelengths are 361.0, 359.0 and 367.0 nm, respectively. Four emission bands due to ^5D4-^7Fj （j = 6, 5, 4, 3 ） transitions were observed for TbLadipy （ H2O ）2 （489.0, 545. 0, 584.0,620.0 nm） and TbL3phen （H2O）2 （490. , 544.0, 583.0, 620.0 nm）. And under the same conditions, only one emission band due to ^5Da-^7F5 transition was observed for TbL2 （TPPO）ENO3. The emission intensity of TbLadipy （H2O）2 is the strongest among the three complexes.

Syntheses, characteristics and fluorescence properties of complexes of terbium with benzoic acid and its derivatives

The binary complexes of terbium with benzoic acid and its derivatives （phthalic acid, iso-phthalic acid, o-aminobenzoic acid, salicylic acid, sulfosalicylic acid） were synthesized and their compositions were identified by elemental analyses. UV, IR of the complexes were investigated. The UV spectra indicate that the complexes’ ultraviolet absorption is mainly the ligands’ absorption, but the location of peak drifts. The IR spectra show that the IR spectra of complexes are different from those of free ligands, and the band at 400500 cm-1, due to the stretching vibration of Tb—O, is absent for free ligands. The fluorescence properties were investigated by using luminescence spectroscope, the results show that all the six complexes of terbium exhibit excellent luminescence, due to the transition from the lowest excited state （）5D4 to （）7F ground state manifold, the complexes of terbium with sulfosalicylic acid have the strongest fluorescence intensity, and is stronger than o-aminobenzoic acid-terbium, whose fluorescence intensity is regarded as the strongest one in the literature, and even stronger than some phosphor of terbium.

Preparation and Characterization of Ternary Europium ComplexDoped Thin SolGel Hybrid Film by Fluorescence Spectroscopy

Ternary europium complex with dibenzoylmethane(DBM)and 1,10phenanthroline(phen)was insitu synthesized in thin SiO2/polyvinyl butyral(PVB)hybrid films by a twostep solgel process and characterized by means of fluorescence spectroscopy.The luminescence spectra,fluorescence lifetimes and photostability were all investigated.The results showed that the hybrid films exhibited the characteristic emission bands of the central rare earth Eu3+.In addition,Eu3+presented longer fluorescence lifetime than in an ethanol solution and the complex had a higher photostability in the hybrid film than in the PVB film containing the corresponding pure complex.

Luminescent Thin Film of Doped Terbium Complex Obtained by Sol-Gel Method

The transparent luminescent thin films of doped terbium complex were obtained by sol gel method. The result indicates that rare earth carboxylates with poor solubility can be homogeneously doped into sol matrix in situ. The fluorescence spectra show that the thin film material emits the characteristic narrow band emission of Tb 3+ under the UV excitation.

Synthesis,crystal structure and characterization of one-dimension complex constructed by terbium(Ⅲ) and 2-iodobenzoate

The complex of [Tb（2-IBA）3（H2O）2]n （2-IBA=2-iodobenzoate） was prepared by solvent method from TbCl3-6H2O and 2-iodobenzoic acid. The crystal structure was determined with X-ray single-crystal diffraction. The X-ray diffraction analysis indicated that the title complex crystallized in triclinic crystal system and Pi space group. The Tb^3＋ ion was coordinated by six oxygen atoms from five 2-IBA ligands and two oxygen atoms from two water molecules, giving a distorted square-antiprism polyhedral geometry. The carboxyl groups were bonded to the Tb^3＋ ions with bidentate-bridging and bidentate-chelating coordination modes. The adjacent Tb^3＋ ions were linked by two bidentate-bridging 2-IBA ligands, forming 1-D chain structure. The fluorescence spectrum of the complex showed four main peaks at 489, 543, 587, and 618 nm, corresponding to ^5D4→^7Fj（J=6-3） transition emissions of the Tb^3＋ ion, respectively.

Synthesis, Structure and Fluorescence Properties of Tb(Ⅲ) Complex with Isonicotinic Acid and Biphenyl-2,2′-Dicarboxylic Acid

Terbium perchlorate reacted with isonicotinic acid （Hpya） and biphenyl-2,2＇-dicarboxylic acid （H2dpa） under hydrothermal condition, a new ternary terbium complex [ Tb （pya） （dpa） （H2O） n （ 1 ） was synthesized. The structure of the ternary complex was determined by X-ray single crystal diffraction and characterized by elemental analysis, fluorescence measurement. The fluorescence spectrum shows the title complex emits strong green light. The crystal data for the com- plex： monoclinic, P21/n space group, a =0.8908（5）nm, b = 1.0569（6）nm, c =2.0969（11）nm, β = 98.446（8）°, V = 1.9528（18） nm^3, Z = 4, R = 0.0241, wR2 = 0.0534. The center Tb3＋ ion is eight coordinated. The coordination polyhedron around Tb3 ＋ ion can be described as a distorted square antiprism. The complex forms an infinite one-dimenand sional alternating chain polymer by bridging carboxyl groups of pyadpa.

Synthesis of a Polyaminopolycarboxylic Acid and Fluorescence of Tb^(3+) Complexes in Aqueous Solution

A new polyaminopolycarboxylic acid, diethylenetriamine N′,N bi( p acetoamino salicylic acid) N′,N″,N triacetic acid(DTPA·2pAS), has been synthesized DTPA·2pAs can sensitize the luminescence of Tb 3+ and Dy 3+ in aqueous solution Fluorescent titration at pH 7 0 indicated a 1∶1 composition of Tb 3+ to DTPA·2pAS for the complexes The complexes exhibit intensely sensitized fluorescence in a range of pH 5 0～12 0 The fluorescence intensity of the complexes increased as the concentration was raised from 1×10 -7 to 1×10 -4 mol/L, and then decreased at 1×10 -3 mol/L due to concentration quenching A replacement of EDTA with DTPA·2pAs in Tb 3+ EDTA complex solution led to increasement in Tb 3+ sensitized luminescence intensity, suggesting formation of Tb 3+ DTPA·2pAS complexes and higher stability of these complexes than those of Tb 3+ EDTA, which has been confirmed by determination of stability constants with pH potentiometric titration The results show that DTPA·2pAS may be applied to fluorescent immunoassay as a “fluorescence enhancement solution”

Novel Terbium Chelate Doped Fluorescent Silica Nanoparticles

Novel terbium chelate doped silica fluorescent nanoparticles were prepared and characterized. The preparation was carried out in water-in-oil （W/O） microemulsion containing monomer precursor （pAB-DTPAA-APTEOS）, Triton X-100, n-hexanol, and cyclohexane by controlling copolymerization of tetraethyl orthosilicate and 3-aminopropyl-triethyloxysilane. The nanoparticles are spherical and uniform in size, about 30 nm in diameter, strongly fluorescent, and highly stable. The amino groups directly introduced to the surface of the nanoparticles using APTEOS during preparation made the surface modification and bioconjugation of the nanoparticles easier. The nanoparticles are expected as an efficient timeresolved luminescence biological label.

Study on fluorescence properties of rare earth complexes influenced by steric effect

The rare earth complexes Tb（o-BrBA）3,Tb（m-BrBA）3 and Tb（p-BrBA）3 were synthesized using o-,m-,p-bromo benzoic acids（2-bromo benzoic acid,3-bromo benzoic acid and 4-bromo benzoic acid） as ligand,respectively.The UV spectra showed that the absorption ability of Tb（m-BrBA）3 was the strongest.However,the fluorescent intensity of Tb（o-BrBA）3 was the weakest.The effect of the molecular structure,the energy level of Tb3＋ and energy transfer efficiency from ligands to Tb3＋ were discussed to explain the experimental results.The results indicated that,due to the large atomic radius of bromine,the steric effect caused by the different substitution bromine on the benzene ring might strongly affect the bond length formed by the coordination atoms and Tb3＋.The longer the bond length was,the lower the efficiency of energy transfer was,and the weaker the fluorescent intensity was.

Research and application of fluorescence system on norfloxacin-terbium-phen-SDBS

Fluorescence characteristics of complex system of rare earth terbium （Tb3＋）, norfloxacin, 1,10-phenanthroline（1,10-phen） and sur- factant sodium dodecyl benzene sulfonate （SDBS） had been studied by using fluorescence spectroscopy. In a buffer solution （pH=6.3）, the fluorescence intensity of the norfloxacin-Tb3＋ （NFLX-Tb3＋） system had been remarkably enhanced by SDBS and 1,10-Phen. When excited at 335 nm, a good linear relationship between fluorescence intensity of NFLX-Tb3＋ system and NFLX concentration was obtained in the range of 8× 10-8-4× 10-6 mol/L, and the linear equation was F=2× 10^8 CNFLX＋22.7 with correlation coefficient of 0.9959. In addition, this method was compared with some previous literatures, the proposed method had relatively higher sensitivity and lower detect limit. The method was sim- ple, rapid, sensitive, practical and suitable for direct analysis of pharmaceutical preparation. It was successfully applied to determine the cap- sules, human serum and urine in real pharmaceutical samples.

高湿度下具有荧光指示功能的PET复合膜的制备与性能

为了制备出能在高湿度、易结雾环境下可持续发光的薄膜,以聚对苯二甲酸乙二醇酯(PET)膜为基底,将具有优异疏水功能的新型稀土发光配合物和聚甲基丙烯酸甲酯(PMMA)均匀分散制成发光涂覆液,通过涂覆刮膜技术,制备出PET-PMMA发光复合膜,并对其进行测试表征。荧光分光光度计和共聚焦显微镜测试的结果表明:发光材料占聚合物PMMA的质量分数为1.50%时所制备的PET发光膜具有良好的表面均匀性和最佳的荧光性能,荧光强度可达到9979 a.u.,在不同激发波长下PET-PMMA发光复合膜均可以显现出发光材料中Eu3+的特征荧光发射峰;测得发光复合膜的最佳紫外激发波长为350 nm,在最佳激发波长下发光复合膜具有较好的色纯度;通过对比发光复合膜浸泡在水溶液7 d内每天的荧光强度值,发现在发光材料仅有1.50%的前提下,样品的荧光强度损失仅有5%,这表明所制备的发光复合膜遇水易猝灭的弊端得到极大改善,这为PET农膜在潮湿、易结雾环境下实现长期稳定的荧光指示功能提供了重要基础。

Synthesis,characteristic and intramolecular energy transfer mechanism of reactive terbium complex in white light emitting diode

A reactive Tb（III） complex with 2-aminobenzoic acid（2-ABAH） and acrylonitrile（AN） as ligands was synthesized.The structure of the complex was characterized by elemental analysis and Fourier transform infrared spectrometry（FT-IR）.The results indicated that the ligands were coordinated with Tb（III） ion.Thermal gravity-derivative thermogravimetric（TG-DTG） analysis indicated that the complex kept stable up to 198 oC.Luminescence properties were investigated by UV-vis absorption spectra and fluorescence spectra.The results suggested that being excited at 361 nm,the complex exhibited characteristic emission of Tb（III） ion,revealing that the complex could be excited by 365 nm ultraviolet chip.The HOMO and LUMO,ΔE（HOMO-LUMO）,molecular frontier orbital,and the singlet state and triplet energy state levels of the ligands were calculated at the B3LYP/6-31＋G（d） level.The results indicated that intramolecular energy transfer mechanism followed Dexter exchange energy transfer theory.Both the calculation for excited state of ligand and energy transfer mechanism could provide the theoretical basis for the design of high luminescent materials of rare earth complexes with organic ligands.

TbCo/Cr Amorphous Film with Perpendicular Magneto-Anisotropy

The amorphous TbCo/Cr films with perpendicular magneto-anisotropy were prepared by nonbiased r.f magnetron sputtering and the effects of Cr underlayer on the magnetic properties of TbCo films were investigated. It is found that both the TbCo layer thickness and the Cr underlayer can influence the magnitude of anisotropy for TbCo films. A perpendicular anisotropy as high as 4.57×10~6 erg·cm^(-3) was obtained in 120 nm thick Tb_(31)C_(69) films with a 180 nm thick Cr underlayer. But it is only 3.24×10~6 erg·cm^(-3) for the Tb_(31)Co_(69) film without Cr underlayer of the same thickness. The cross-sectional SEM observations indicate that the TbCo films with Cr underlayer consist of columns structure. It is considered that this heterogeneous structure gives rise to the anisotropy enhancement of TbCo films in case with Cr underlayer.

铽荧光配合物小颗粒悬浮液显现潜在手印的研究

以稀土铽、对甲基苯甲酸、邻菲罗啉为原料合成铽三元荧光配合物,以水为溶剂,加入表面活性剂和铽配合物制成小颗粒悬浮液,用于常见非渗透性客体表面潜在手印的显现,并对悬浮液显现手印条件进行优化。结果显示合成的铽荧光配合物在365 nm紫外灯照射下发出绿色荧光;配置悬浮液显出手印纹线清晰,细节特征明显;材料具有优异荧光特性和广泛适用性。

PET发光复合膜的制备工艺与荧光性能优化

为制备具有良好光致发光功能的聚对苯二甲酸乙二醇酯(PET)发光复合膜,以PET薄膜为基材,通过物理喷涂技术将荧光强度较好的有机稀土发光材料均匀分布在PET膜表面,制备PET发光膜;在PET发光膜表面引入不同聚合物的防护功能层,制备PET发光复合膜,并进行荧光性能测试与表征。结果表明:发光喷涂溶液质量分数为1.50%时所制备的PET发光膜具有最佳的荧光性能,且发光材料在膜表面分散均匀;选用PVDF为防护功能层所制备的PET-PVDF发光复合膜荧光强度最高,达3158 a.u.,而且在不同激发波长下PETPVDF发光复合膜均可以显现出发光材料中Eu^(3+)的特征荧光发射峰;PET-PVDF发光复合膜的最佳紫外激发波长为301 nm,在最佳激发波长下PET-PVDF发光复合膜具有较好的色纯度,可以显现出靓丽的红光。

铽-金属有机框架改性棉织物的制备及其pH值探测性能

为解决金属有机框架材料(MOFs)易团聚不易回收的问题,同时提高其利用率,以棉织物为基底制备了柔性荧光pH值传感材料。利用具有荧光性能的稀土金属Tb与相应配体并添加阻断剂制备微纳米Tb-MOFs,通过热压法将Tb-MOFs粉末负载在棉织物表面,表征其表面形貌、晶体结构和荧光性能等,并分析了其pH值探测性能。结果表明:棉织物表面形成了致密的微纳米Tb-MOFs薄膜,且与粉末状态的Tb-MOFs晶体形态一致;Tb-MOFs改性棉织物(Tb-MOFs-CF)在365 nm波长的紫外光照射下发出明亮的蓝绿色荧光,其荧光强度显示出了很强的pH值依赖性;Tb-MOFs-CF在510 nm处的荧光强度与缓冲溶液的pH值呈线性关系,线性响应范围为pH值1~5,且对于酸性、碱性与中性的溶液其酸碱度检测具有较快的响应性。

铽与苯甲酸及其衍生物配合物的合成与发光特性

合成了铽与苯甲酸及其衍生物(苯甲酸、邻苯二甲酸、间苯二甲酸、水杨酸、邻氨基苯甲酸、磺基水杨酸)的配合物。经元素分析确定其组成结构式。研究了它们的红外吸收光谱、紫外吸收光谱及荧光光谱。紫外光谱的研究表明,配合物的紫外吸收主要表现为配体的吸收;红外光谱的研究表明,配合物的红外光谱不同于自由配体的红外光谱;荧光光谱的研究表明,铽与这六个配体的配合物都表现出较好的荧光性能,并发现磺基水杨酸铽配合物在本实验系列中其荧光发射最强。

稀土配合物-PAA-g-PE膜的荧光光谱

通过紫外光接枝聚合反应 ,将丙烯酸 (AA)接枝于PE膜表面 ,在一定 pH值条件下 ,使接枝膜与Eu3+、α 噻吩甲酰三氟丙酮 (TTA)的乙醇 水溶液或Tb3+、乙酰丙酮 (AcAc)的氯仿 水溶液作用 ,制得红色或绿色荧光膜。与相应的Eu(TTA) 3·(H2 O) 2 或Tb(AcAc) 3·(H2 O) 2 固态配合物相比 ,荧光膜的激发和发射光谱都发生了明显的变化 ,可以推测 ,稀土配合物与高分子材料之间发生了化学键结合。此外 ,还对荧光膜的红外光谱进行了观察。

邻、间、对甲氧基苯甲酸铽与1,10-邻菲啰啉三元配合物的合成和发光性能

以邻、间、对甲氧基苯甲酸(o MOBA,m MOBA,p MOBA)为第一配体,以1,10邻菲啰啉(phen)为第二配体,合成了三种甲氧基苯甲酸铽(Ⅲ)与1,10邻菲啰啉的三元配合物ü胤治觥⑴湮坏味ǚ治?确定了配合物的组成分别为Tb(o MOBA)3phen·H2O、Tb(m MOBA)3phen·H2O和Tb(p MOBA)3phen。通过红外光谱对配合物的结构进行了表征,结果表明在配合物中羧基氧原子和邻菲啰啉中的氮原子均参与了配位ü夤馄追治?探讨了第一配体取代基位置的变化,对三元配合物的发光性能的影响。结果表明,三种配合物均具有优良的光致发光性能,各配合物的相应跃迁发射峰位基本上没有变化,5D4→7F6、5D4→7F5两个较强发射峰的强度顺序为:Tb(o MOBA)3phenoH2O>Tb(m MOBA)3phenoH2O>Tb(p MOBA)3phen。