铽(Ⅲ)配合物的合成及其光谱分析

分别以1,10-邻菲啰啉、三苯基氧膦,2,2'-联吡啶为第二配体,并以苯甲酰丙酮为第一配体,合成了3种铽(Ⅲ)配合物.通过元素分析和红外吸收光谱确定了其结构,并利用紫外-可见吸收光谱和荧光光谱,研究其发光机理.研究结果表明,3种铽(Ⅲ)配合物的光吸收以第一配体为主,激发下均能发射Tb3+的5D4→7F4的电子跃迁特征峰...     

芳香羧酸类铕(Ⅲ)三元有机配合物的合成与荧光性质

以苯甲酸(BA)、邻氨基苯甲酸(o-Amino)、邻苯二甲酸(o-Phth)及水杨酸(Sal)4种芳香族羧酸为第一配体,以邻菲咯啉(Phen)为第二配体,通过溶液沉淀法合成了4种稀土铕(Ⅲ)三元有机配合物.通过元素分析、红外光谱、紫外吸收光谱分析等方法确定了它们的组成结构,用荧光光谱研究分析了4种配合物的光致发光荧光性能,初步探讨了不同第一配体对铕(Ⅲ)三元配合物荧光性质影响,并筛选出具有很好应用价值的红色高亮有机荧光材料.     

铕(Ⅲ)-4-VP光致发光稀土配合物单体的制备

以 4 乙烯基吡啶 (4VP)、邻菲洛啉 (Phen)为配体 ,与EuCl3 在乙醇溶液中一步合成了含有双键的三元稀土配合物 ,通过紫外光谱与荧光光谱的测定 ,研究稀土配合物光致发光的机理。结果表明 ,4 乙烯基吡啶通过吡啶环上的氮原子与稀土离子可直接配位 ;邻菲洛啉配体具有协同配位效应。稀土配合物较EuCl3 的荧光发射强度提高了 12倍之多。     

铕配合物的合成及其荧光防伪油墨的制备

选用苯甲酸(BA)、噻吩甲酰三氟丙酮(TTA)、邻菲咯啉(Phen)作为配体合成了Eu(BA)3Phen三元配合物、Eu(BA)(TTA)2Phen四元配合物,将其作为荧光剂,制备了稀土荧光防伪油墨。红外光谱的分析表明配体与铕离子发生了配位。测定了配合物和荧光防伪油墨的荧光性能,发射波长为614 nm,制备的稀土荧光防伪油墨在可见光下印迹无色,在紫外灯下呈现明显红色荧光。     

铽与苯甲酰丙酮和邻菲哕啉配合物的合成及性能研究

合成了以苯甲酰丙酮为第一配体，1，10-邻菲哆啉为第二配体的一种铽的三元配合物Tb（BAC）3Phen,通过元素分析确定了其组成，并用红外吸收光谱、紫外。可见光吸收光谱、差热-热重曲线、原子力显微镜对其进行了表征，同时研究了Tb（BAC）3Phen的光致发光性能。实验结果表明配体苯甲酰丙酮和1，10-邻菲哆啉能够较好地敏化中心离子Tb^3-发光，Tb（BAC）3Phen的最大发射波长为615nm，并具有良好的热稳定性和成膜性，是一种黄白光发光材料。     

铕、铽-α(β)-萘酸-邻菲哕啉三元配合物的合成及性质研究

分别以α-萘甲酸(α-HNMA)、β-萘甲酸(β-HNMA)、α-萘乙酸(α-HNAA)、β-萘乙酸(β-HNAA)为第一配体,1,10-邻菲啰啉(phen)为第二配体,合成了4种Eu(Ⅲ)和4种Tb(Ⅲ)的三元配合物.通过元素分析、配位滴定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,发现各配体的特征吸收峰(VC=O、VC=N)在形成配合物后不同程度地向低波数方向移动,说明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.采用TG-DTG技术对8种配合物的热分解过程进行了研究,8种配合物均有较好的热稳定性.室温下测得了各配合物粉末的激发和发射光谱,结果表明,4种铕的三元配合物均发出红色荧光,最强发射峰613 m附近的强度顺序为Eu(β-NMA)3phen＞Eu(α-NMA)3phen·H2O＞Eu(α-NAA)3phen＞Eu(β-NAA)3phen·H2O.4种铽的三元配合物无明显的荧光现象.     

铕、铽-α(β)-萘酸-邻菲啰啉三元配合物的合成及性质研究

分别以α-萘甲酸(α-HNMA)、β-萘甲酸(β-HNMA)、α-萘乙酸(α-HNAA)、β-萘乙酸(β-HNAA)为第一配体,1,10-邻菲啰啉(phen)为第二配体,合成了4种Eu(III)和4种Tb(III)的三元配合物。通过元素分析、配位滴定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,发现各配体的特征吸收峰(νC=O、νC=N)在形成配合物后不同程度地向低波数方向移动,说明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?捎肨G-DTG技术对8种配合物的热分解过程进行了研究,8种配合物均有较好的热稳定性。室温下测得了各配合物粉末的激发和发射光谱,结果表明,4种铕的三元配合物均发出红色荧光,最强发射峰613 nm附近的强度顺序为:Eu(β-NMA)3phen>Eu(α-NMA)3phen.H2O>Eu(α-NAA)3phen>Eu(β-NAA)3phen.H2O。4种铽的三元配合物无明显的荧光现象。     

镧掺杂铕的2,5-噻吩二羧酸-1,10-菲咯啉四元异核配合物的合成、表征及谱学性质

合成了5种新型镧掺杂铕的2,5-噻吩二羧酸(H2L)、1,10-菲咯啉(Phen)四元异核配合物,通过元素分析、TG-DTA、红外光谱法确定其组成为(EuxLay)2L3(Phen)2·4H2O(x∶y=0.90∶0.10、0.70∶0.30、0.50∶0.50、0.30∶0.70、0.10∶0.90),配体的羧基与稀土离子以螯合双齿配位。荧光光谱测试表明镧对铕的配合物有荧光浓聚效应。     

2,2,2-胺三乙酰-吡啶及其稀土配合物的合成、表征与荧光性质

为了研究三脚架型配体与其稀土配合物荧光性质的关系,合成了三脚架型配体--2,2,2-胺三乙酰-吡啶及其6种稀土配合物.通过元素分析、摩尔电导、红外光谱、核磁共振波谱、差热-热重分析和荧光光谱等分析手段对配体及其稀土配合物的组成、性质进行了表征.结果表明,配合物的组成为Re(NO3)3·L·6H2O(Re=Ce3 ,Sm3 ,La3 ,Tb3 ,Y3 ,Eu3 );在DMF中属于2:1型电解质,其中,配合物中既存在以单齿形式与中心离子配位的NO-3,也存在游离的NO-3.荧光光谱分析表明,Tb(Ⅲ)配合物具有较强的Tb3 特征线状荧光,说明T(L)→5D4(Tb)的能级较匹配,从而使Tb3 荧光发射大大增强.同时,研究了溶剂中荧光增强效应,说明在极性较强、中性体系中配体对Tb3 的敏化作用较强.     

苯二甲酸铽与1,10-邻菲啰啉三元配合物的合成及性质

以邻(间、对)苯二甲酸[o(m、p)-PA]和1,10-邻菲啰啉(phen)为配体,合成了5种Tb(III)的三元配合物。各配合物的组成分别为:Tb2(m-PA)3(phen)2.6 H2O、Tb2(p-PA)3(phen)2.2 H2O、Tb2(o-PA)3phen.4 H2O、Tb2(m-PA)3phen.4 H2O和Tb2(p-PA)3phen.4 H2O。红外光谱分析表明,在各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。5种配合物均有较好的热稳定性,它们的热稳定性顺序为:Tb2(m-PA)3(phen)2.6 H2OTb2(p-PA)3(phen)2.2 H2OTb2(m-PA)3phen.4 H2OTb2(o-PA)3phen.4 H2OTb2(p-PA)3phen.4 H2O。在室温条件下,5种铽的三元固体配合物均发出绿色荧光,它们在最佳发射峰5D4→7F5(545nm)时的荧光强度顺序为:Tb2(p-PA)3phen.4 H2OTb2(m-PA)3(phen)2.6 H2OTb2(p-PA)3(phen)2.2 H2OTb2(m-PA)3phen.4 H2OTb2(o-PA)3phen.4 H2O。     

Structure and photoluminescence property of complexes of aromatic carboxylic acid-functionalized polysulfone with Eu(Ⅲ) and Tb(Ⅲ)

With chloromethylated polysulfone as starting substance, naphthoic acid (NA) and benzoic acid (BA) were bonded onto the side chains of polysulfone (PSF) via polymer reactions, obtaining two kinds of aromatic carboxyl acid-functionalized polysulfone, PSFNA and PSFBA. Subsequently, the luminescent binary and ternary polymer-rare earth complexes of Eu(Ⅲ) and Tb(Ⅲ) were prepared through coordination reactions, respectively, with PSFNA and PSFBA as macromolecule ligands and with 1,10-phenanthroline (Phen) and 4,4′-bipyridine (Bipy) as small-molecule co-ligands. This work focuses on investigating the relationship between structure and photoluminescence property of these complexes. The experimental results indicate that the macromolecule ligands PSFNA and PSFBA can strongly sensitize the fluorescence emissions of Eu³⁺ ion or Tb³⁺ ion, and the sensitization effect is strongly dependent on the structure of the ligands and the property of the central ions. The fluorescence emission of the binary complex PSF–(NA)₃–Eu(Ⅲ) is stronger than that PSF–(BA)₃–Eu(Ⅲ), suggesting the bonded ligand NA has stronger sensitization action for Eu³⁺ ion than ligand BA; The binary complex PSF–(BA)₃–Tb(Ⅲ) emit very strong characteristic fluorescence of Tb³⁺ ion, displaying that ligand BA can strongly sensitize Tb³⁺ ion, whereas PSF–(NA)₃–Tb(Ⅲ) does not emit the characteristic fluorescence of Tb³⁺ ion, showing that the bonded ligand NA does not sensitize Tb³⁺ ion. The fluorescence intensity of the ternary complexes is stronger than that of the binary complexes in the same series. The solid films of these complexes also emit the strong characteristic fluorescence of Eu³⁺ ion or Tb³⁺ ion.     

稀土(铕、铽)三元配合物的合成、表征与发光性能

合成了Eu(TFA)3(TPPO)2、Tb(TFA)3(TPPO)2三元配合物以及Eu1／2Tb1／2(TFA)3(TPPO)2三元双核配合物，并经元素分析、紫外-可见吸收光谱和红外透射光谱确认。研究了配合物的发光性质,发现了该三元体系配合物的摩擦发光现象,且三元双核配合物经摩擦发出明亮的白光。     

Synthesis,structural, thermal and optical studies of rare earth coordinated complex: Tb(Sal)3Phen

Complexes of salicylic acid (Sal) and 1,10-phenanthroline (Phen) were synthesized coordinated with terbium ion (Tb³⁺) in crystalline phases. The structural characterizations of the lanthanide complex were made using FT-IR, NMR (¹H and ¹³C) and XRD techniques. These measurements confirm the formation of Tb(Sal)₃Phen complex structure. The thermal aspects of the complex were examined using DTA and TGA techniques. An enhancement in luminescence intensity of Tb³⁺ ion bands were observed in Tb(Sal)₃Phen complex as compared to TbCl₃ crystals on 355 nm laser excitation. Enhancement is reported due to the efficient energy transfer process from Sal to Tb³⁺ ions. This is also confirmed by the time resolved photoluminescence spectroscopy with increase in lifetime of Tb³⁺ ions due to encapsulation in Sal/Phen network. Our system in itself can be a deserving candidate for luminescent solar collector material when coupled with solar cells.     

苯二甲酸铽与1,10-邻菲哕啉三元配合物的合成及性质

以邻(间、对)苯二甲酸[o(m、p)-PA]和1,10_邻菲啰啉(phen)为配体,合成了5种Tb(Ⅲ)的三元配合物.各配合物的组成分别为:Tb_2(m-PA)_3(phen)_2·6H_2O、Tb_2(p-PA)_3(phen)_2·2H_2O、Tb_2(o-PA)_3phen·4H_2O、Tb_2(m-PA).phen·4H_2O和Tb_2(p-PA)_3phen·4H_2O.红外光谱分析表明,在各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住.5种配合物均有较好的热稳定性,它们的热稳定性顺序为:Tb_2(m-PA)_3(phen)_2·6H_2O>Tb_2(p-PA)_3(phen)_2·2H_2O>Tb_2(m-PA)_3phen·4H_2O>Tb_2(o-PA)_3phen·4H_2O>Tb_2(p-PA)_3phen·4H_2O.在室温条件下,5种铽的三元固体配合物均发出绿色荧光,它们在最佳发射峰~5D_4→~7F_5(545nm)时的荧光强度顺序为:Tb_2(p-PA)_3phen·4H_2O>Tb_2(rn-PA)_3(phen)_2·6H_2O>Tb_2(p-PA)_3(phen)_2·2H_2O>Tb_2(m-PA)_3phen·4H_2O>Tb_2(o-PA)_3phen·4H_2O.     

Improved luminescence properties of europium complexes encapsulated into mesoporous SBA-15

Two kinds of Eu3+ COmplexes-Eu(TTA)3(TPPO)2 (TTA: thenoyltrifluoroacetone, TPPO: triphenylphosphineoxide) and Eu(BA)3(TPPO)2 (BA: 1-benzoylacetone)-were fully encapsulated, uniformly distributed into the channels of unmodified and modified SBA-15, and structurally characterized. The luminescent properties of the encapsulated complexes were systematically studied in contrast to the pure complexes. The results indicate that the excitation bands assigned to the pi-pi* electron transition of the ligands for Eu3+ complexes encapsulated in SBA-15 were split into different components, and the 5D0-7F0 transitions became partly allowed. The emission lines for the 5D0-7F2 transitions became broader and the relative intensity for different crystal field components varied greatly in comparison to the pure complex. Most importantly, the photostability and thermostability of the emissions improved considerably.     

{[Tb(L)2(H2O)2](Hdmpy)(H2O)2｝∞/丙烯酸酯类聚氨酯稀土高分子材料的制备及性能研究

以9,10-双蒽酸(H2L)和2,6-二甲基吡啶(Hdmpy)为配体,合成了一个二维结构的稀土配合物{[Tb(L)2(H2O)2] (Hdmpy) (H2O)2｝∞;用原位聚合法将该稀土配合物与丙烯酸类聚氨酯大分子单体复合,制备出{[Tb(L)2(H2O)2](Hdmpy)(H2O)2｝∞/丙烯酸酯类聚氨酯稀土高分子材料,并研究了稀土配合物在材料中的分散及材料的热稳定性、荧光性能等.研究结果表明,配合物在稀土高分子材料中主要以200～500nm颗粒均匀分散;且该材料具有良好的热稳定性能(＞300℃),在波长372nm的激发光下,材料在440nm出现最大荧光发射峰,有望应用于发光材料领域.     

Crystal structure of a complex of Pu(VI) nitrate with triphenylphosphine oxide, [PuO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>(OP(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)<Subscript>3</Subscript>)<Subscript>2</Subscript>]

Single crystals of [PuO₂(NO₃)₂(TPPO)₂] (TPPO = OPPh₃) isostructural to the related compounds of uranyl and neptunyl were isolated, and the structure of this complex was determined. Contrary to the complexes [AnO₂(TPPO)₄](ClO₄)₂ studied previously, the interatomic distances and volumes of coordination polyhedra of An in these compounds somewhat decrease in the series U-Np-Pu. This difference was attributed to a change in the number of TPPO ligands in the compounds and weakening of their interaction with oxygen atoms of the AnO ₂ ²⁺ groups in passing from [AnO₂(TPPO)₂](ClO₄)₂ to [AnO₂(No₃)₂(TPPO)₂].     

Synthesis and luminescence properties of ternary complexes of Sm x Tb1−x (TTA)3Phen nanoparticles and their surface modification

A series of Sm _x Tb_1?x (TTA)₃Phen (x = 1.0, 0.9, 0.7, 0.5, 0.3, 0.1, 0) complexes was synthesized by wet chemical method and characterized using Fourier transform infrared spectroscopy and fluorescence spectroscopy. The IR absorption spectra indicate that α-thenoyltrifluoroacetone was coordinated to the rare earth ions and that chemical bonds were formed between rare earth ions and the nitrogen atoms in 1,10-Phenanthroline (Phen). The fluorescence spectra of the complexes indicate that the emission intensity of Sm³⁺ was enhanced by the addition of substitutive Tb³⁺. These data show that not only the ligands (TTA and Phen) but also Tb³⁺ could absorb and transmit energy to Sm³⁺ in the complexes. Formation of dual-core complexes appears to be responsible for co-fluorescence, which can greatly promote the illuminant ability of Sm (TTA)₃Phen complex. After further encapsulation by SiO₂, the Sm _x Tb_1?x (TTA)₃Phen@SiO₂ core–shell structure was very stable to UV light.