铕掺杂配合物的合成及其荧光性质研究

采用稀土掺杂的方法以Zn2+与Eu3+、配体对氯苯甲酸(CBA)、邻菲罗啉(Phen)合成铕掺杂配合物铕-锌-对氯苯甲酸-邻菲罗啉(Eu-Zn-CBA-Phen).经元素分析,推测其组成为:Eu1-xZnx(CBA)3-xPhen*H2O(x=0～0.8).红外光谱分析证实,铕与配体发生配位,而紫外与荧光光谱分析表明,随着Zn2+取代配合物中部分Eu3+,配合物的荧光强度明显增加,当掺杂Zn2+与Eu3+摩尔分数比为2∶3时,荧光强度达到最大值.同时还系统地考察了非稀土金属离子的加入对配合物荧光性能的影响和荧光增强机理.     

稀土铕配合物Eu（BTF）3phen的制备及其性质研究

采用常温搅拌法制备了配合物Eu(BTF)3phen(BTF=苯甲酰三氟丙酮,phen=邻菲罗啉),改善稀土铕配合物的荧光性能。对配合物的热稳定性和荧光性质进行了测定,结果表明其具有良好的热稳定性,在362 nm激发光激发下,能发射强烈的、来自于Eu3+离子的特征红光,最大发射峰在612 nm,半峰宽大约为8 nm。对邻菲罗啉中性配体进行了两种不同的分子修饰,荧光光谱测试表明,邻菲罗啉配体上引入不同数目的基基团,在一定程度上改善了Eu(BTF)3phen配合物的荧光性能。     

稀土铕,铽β-二酮配合物的合成与发光性能

采用Claisen缩合反应合成了一种新型的β-二酮化合物1-(4-溴苯)-3-苯基丙烷-1,3-二酮(L),并以其为第一配体,邻菲罗啉(phen)为第二配体,合成出新型稀土铕,铽二元及三元配合物。通过元素分析、红外光谱、紫外光谱、荧光光谱对合成的配体及配合物进行了表征。元素分析确定了配合物的组成。红外光谱的分析表明第一配体L中的氧原子以及第二配体phen中的氮原子与稀土离子进行了配位。紫外光谱表明第一配体L为能量的给体,第二配体phen起协同作用。通过荧光光谱研究了配合物的发光性质,结果显示三元配合物的发光强度大于二元配合物,三元配合物Eu(L)3phen表现出Eu3+的特征发射,在593,615,653,701 nm处的发射峰分别归属于Eu3+的5D0→7Fj(j=1,2,3,4)能级间的跃迁,并且以位于615 nm处的5D0→7F2电子跃迁所发出的荧光强度最大;而铽配合物中并没有出现Tb3+的特征发射。进一步的研究表明,这是由于配体L的最低三重态能级较适合Eu3+的发射能级,配体L吸收的能量可以有效的通过Antenna效应传递给稀土中心离子,使得三元配合物Eu(L)3phen的发光强度较大。     

1-(9-蒽基)-3-三氟甲基-1,3-丙二酮邻菲罗啉镱(Ⅲ)配合物的合成及性质研究

设计合成了新的β-二酮配体1-(9-蒽基)-3-三氟甲基-1,3-丙二酮,并与Yb~(3+)和第二配体邻菲罗啉(phen)配位,形成二元配合物YbA_2·2H_2O和三元配合物YbA_3phen,通过元素分析、红外光谱、紫外光谱及荧光光谱对其进行了表征,结果表明,在二元配合物YbA_2·2H_2O和三元配合物YbA_3phen中,都没有出现Yb~(3+)的特征发射峰,配合物的荧光属于配体发光,但是三元配合物YbA_3phen的发光效率要强于二元配合物YbA_2·2H_2O,这与第二配体邻菲罗啉的引入有关。     

均苯三甲酸邻菲罗啉稀土配合物的合成、表征及荧光性质

分别合成了以均苯三甲酸(H3BTC)和邻菲罗啉(phen)为配体,以Sm、Eu、Tb和Dy为中心的4种稀土三元配合物,通过元素分析及稀土络合滴定确定了配合物的组成为RELL'1.5 ·2H20(L=BTC,L'= phen);配合物的红外光谱、紫外光谱和荧光光谱测定结果表明,配合物中均苯三甲酸根的羧基氧原子和邻菲罗啉的氮原子均与稀土离子配位成键;四种配合物均可发出稀土离子的特征荧光,铕、铽配合物具有良好的荧光性能,钐、镝配合物也发出较强的特征荧光.     

铕-芳香族有机羧酸-邻菲罗啉配合物的合成和荧光性能的研究

合成了铕 芳香族有机羧酸 (苯甲酸、邻苯二甲酸 )和邻菲罗啉的二元、三元配合物 ,研究了它们的荧光光谱、红外光谱、紫外可见光谱。结果表明 ,铕和苯甲酸、邻苯二甲酸邻菲罗啉生成的二元、三元配合物 ,在紫外光激发下均可发出铕的特征荧光 ,且三元配合物的荧光强度明显大于二元配合物。     

铽-环丙沙星纳米稀土配合物合成、表征及发光性质研究

制备了纳米铽-环丙沙星-邻菲啰啉稀土配合物,通过元素分析、热重差热分析、X射线衍射(XRD)、红外光谱、紫外光谱对配合物的组成、结构进行了表征,研究了配合物溶解性、热稳定性、发光性能和邻菲啰啉第二配体加入对铽-环丙沙星体系荧光性质的影响。荧光光谱的研究表明,环丙沙星通过分子内能量传递将部分能量传递给铽离子,同时邻菲啰啉的加入能有效地增强铽离子发光强度,配合物具有良好的发光性能,在紫外光激发下显示出Tb3+的特征发射峰,发出很强的绿色荧光。     

N-二茂铁甲酰基甘氨酸邻菲咯啉稀土三元配合物的合成、表征及抑菌活性研究

分别合成了以N-二茂铁甲酰基甘氨酸(Fc-CO-Gly-OH)和邻菲咯啉(phen)为配体,以La3+、Sm3+、Gd3+和Er3+为中心的4种稀土三元配合物,通过元素分析及稀土络合滴定确定了配合物的组成为REL3L’.2H2O(RE=La3+、Sm3+、Gd3+、Er3+,L=Fc-CO-Gly-O,L’=phen);配合物的红外光谱、紫外光谱测定结果表明,配合物中N-二茂铁甲酰基甘氨酸根的羧基氧原子和邻菲咯啉的氮原子均与稀土离子配位成键;抑菌实验表明,配合物对大肠杆菌、金黄色葡萄球菌和伤寒杆菌这3个菌种都有比较好的抑制效果。     

稀土三氯醋酸盐与5—硝基邻菲罗啉配合物的合成与表征

本文报道了稀土三氯醋酸盐与5硝基邻菲罗啉配合物的合成。并通过无素分析、红外光谱、紫外光谱、电导和差热热重分析确证配合物的组成为Ln(CCl_3COO_3(5-NO_2Phen))·C_2H_5OH。     

铕-苯甲酸-1,10-菲咯啉的合成及谱学性质

合成了稀土元素铕( )-苯甲酸-1,10-菲咯啉的三元配合物。通过元素分析和红外光谱确定了配合物的组成为EuL3phen(L∶苯甲酸根,phen∶1,10-菲咯啉)。通过发射光谱和激发光谱的测试表明,三元配合物在579、591、614、649、690nm处产生发射峰,分别归属于Eu3+的5D0→7F0、5D0→7F1、5D0→7F2、5D0→7F3、5D0→7F4跃迁。从发射光谱的峰强和激发光谱在200nm～380nm范围内产生宽而强的吸收峰可以得出第二配体phen的加入能显著增加Eu3+的发光强度,由此说明phen的加入更有利于配体吸收能量,也有利于配体更有效地向Eu3+传递能量。另外,对三元配合物的远红外光谱和拉曼光谱进行了分析。     

Study on Copolymer of PMMA with Eu Complex

The europium complex, Eu3 -1,10-phenanthroline (Phen) -acrylic acid (AA) was prepared and its structural formula is Eu(Phen) (AA)3. The high luminescence rare earth polymer materials were obtained by the copolymerization of europium complex with methyl methacrylate using AIBN as an initiator. The copolymer structure and properties were characterized by FT-IR, UV-Vis, RF spectra and thermogravimetric analysis (TG). Results indicate that block copolymer is synthesized. Fluorescent property shows that Eu copolymer emits rare earth fluorescence and the emission intensity increases with the rise in Eu content and reaches a maximum value.     

Syntheses and Characterization of Binuclear Complexes Tb（1-x）Eux（TTA）3 Phen

Rare earth ternary complexes Tb1-xEux（TTA）3Phen（x=0,0.25,0.5,0.75,1.0）were synthesized and characterized by DTA-TG,XRD and infrared（IR）.The photophysical properties of these complexes were studied in detail using ultraviolet absorption spectra and fluorescent spectra.Ultraviolet absorption showed that the energy absorption of the complexes mostly came from ligands.Infrared spectra of Tb1-xEux（TTA）3Phen complexes were similar to the pure complexes.TG curves proved that the complexes were stable.Tb3＋ emission was almost quenched and the Eu3＋ emission was enhanced by codoping the complexes.The Tb3＋ ion acted as an energy transfer bridge that helped energy transfer from poly（N-vinylcar-bazole（PVK）to Eu3＋.In addition,their PL and EL properties were systematically studied.     

Synthesis, Characterization and Fluorescence of Rare earth Nitrate Complexes with Triaza-crown Ether Derivative

Sinceaza crownethershowsspecialcoordinationpropertiestotransitionmetalandheavymetalions[1,2 ] ,therearemanyreportsofthecomplexesinhost guestchemistry ,molecularrecognition[3 ,4] andionophoreinmembranetransportation[5] ,butthereislittlereportontheirrareearthscomplexesandthefluorescenceaboutthecomplexes[6] ,andthefluorescenceintensityoftheircomplexesarenotverystrong .Weinsetbenzoylgroupintothemacrocycle ,expectingthatitsrareearthscomplexeshavebetterfluorescenceproperties .Inthispaperthesynthesis…     

Fluorescence and Judd-Ofelt analysis of rare earth complexes with maleic anhydride and acrylic acid

Two kinds of Eu-complexes, Eu(TTA)2(Phen)(AA) and Eu(TTA)2(Phen)(MA) (HTTA=2-Thenoyltrifluoroacetone, Phen=1,10- phenanthroline, AA=acrylic acid, MA=Maleic anhydride), which combined the excellent fluorescence properties of Eu(TTA)2(Phen)(H2O) and the reactivity of acrylic acid and maleic anhydride with radicals, were synthesized. The two complexes were characterized by elemental analysis, infrared (IR) spectra, and X-ray photoelectron spectroscopy (XPS). Based on the data shown from the fluorescent spectra of the Eu-MA and Eu-AA complexes, the ?λ (λ=2 and 4) experimental intensity parameters were calculated. The results demonstrated that the ?2 intensity parameters for the two complexes were smaller than those for the Eu(TTA)2(Phen)(H2O) complex, indicating that a less symmetri- cal chemical environment existed in the complexes. It implied that the radiative efficiency of the 5D0 of these two complexes could be en- hanced by ligand of MA and AA, respectively. The luminescent lifetime of the Eu-AA (τ=7.26×10–4 s) or Eu-MA complex (τ=8.12×10–4 s) was higher than that of the Eu(TTA)2(Phen)(H2O) complex, which was attributed to the substitution of the water molecule (H2O) in Eu(TTA)2(Phen)(H2O) by the MA or AA ligand.     

Synthesis, fluorescence properties of Eu(Ⅲ) complexes with novel carbazolefunctionalized β-diketone ligand

A novel carbazole functionalized β-diketone, methyl 6-(9-ethylcarbazole-3-yl)-oxoacetyl-2-pyridinecarboxylate (MEP), and its Corresponding Corresponding binary Eu(Ⅲ) complexes Eu(MEP)32H2O and ternary complex Eu(MEP)3Phen with 1,10-Phenanthroline (Phen) were pre-pared. The ligand was characterized based on elemental analysis, FT-IR, and 1H NMR, and the complexes were characterized with elemental analysis, FT-IR and thermogravimetric and differential thermal analysis (TG-DTA). The investigation of fluorescence properties of the com-plexes Eu(MEP)32H2O and Eu(MEP)3Phen showed that the Eu(Ⅲ) ion could be sensitized efficiently by the ligand to some extent, in par-titular, in the ternary system, the secondary ligand Phen acting as a light-harvesting center was involved in the highly efficient energy transfer process, and the emission was stronger than the binary complex. In addition, the introduction of the carbazole moiety enlarged the π-conjugated system of the ligand and enhanced the luminescent intensity of the complexes.     

Synthesis, fluorescence properties of Eu（III） complexes with novel carbazole functionalized β-diketone ligand

A novel carbazole functionalized β-diketone, methyl 6-(9-ethylcarbazole-3-yl)-oxoacetyl-2-pyridinecarboxylate (MEP), and its corresponding binary Eu(III) complexes Eu(MEP)₃·2H₂O and ternary complex Eu(MEP)₃Phen with 1,10-Phenanthroline (Phen) were prepared. The ligand was characterized based on elemental analysis, FT-IR, and ¹H NMR, and the complexes were characterized with elemental analysis, FT-IR and thermogravimetric and differential thermal analysis (TG-DTA). The investigation of fluorescence properties of the complexes Eu(MEP)₃·2H₂O and Eu(MEP)₃Phen showed that the Eu(III) ion could be sensitized efficiently by the ligand to some extent, in particular, in the ternary system, the secondary ligand Phen acting as a light-harvesting center was involved in the highly efficient energy transfer process, and the emission was stronger than the binary complex. In addition, the introduction of the carbazole moiety enlarged the π-conjugated system of the ligand and enhanced the luminescent intensity of the complexes.     

Luminescence of Eu(MBA)_2NO_3Phen Complexes

ＬｕｍｉｎｅｓｃｅｎｃｅｏｆＥｕ（ＭＢＡ）_２ＮＯ_３ＰｈｅｎＣｏｍｐｌｅｘｅｓＪｉｎＬｉｎ－ｐｅｉ（金林培）；ＴｏｎｇＪｉｎ－Ｑｉａｎｇ（童金强）；ＷａｎｇＭｉｎｇ－Ｚｈａｏ（王明昭）；（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＢｅｉｊｉｎｇＮｏ...     

Crystal Structure and Luminescence Spectra of Novel Coordination Layer of {[Eu(m-BDC)(NO3)(Phen)(H2O)]2·2CH3CH2OH}n

The crystal structure of a novel Eu3 coordination polymer, {[Eu(m-BDC)(NO3)(Phen)(H2O)]2 · 2CH3CH2OH}n (m-BDC=1,3-benzenedicarboxylate, Phen=1, 10-phenanthroline), was obtained and its high-resolution luminescence spectra at 77K were measured. The μ2-carboxylate of m-BDC constructs the binuclear building block in which each Eu3 ion is coordinated by four oxygen atoms of m-BDC anions, one oxygen atom from water molecule, two oxygen atoms of nitrate and two nitrogen atoms of Phen, respectively. The μ1-carboxylate of m-BDC conjugates the binuclear units one-dimensional chain or a ribbon, while the hydrogen bonds between ribbons assemble the structure two-dimensional layer with a thickness equaling to the width of the ribbon. The luminescence spectra reveal that the two Eu3 ion sites in the binuclear building blocks have slight environmental difference. The C1 local symmetry of Eu3 ion is concluded from both crystal structure measurement and luminescence spectra.     

两种新的铕配合物的合成、表征及其光、热、电性质

以邻苯二甲酸酐、二苯胺、4-氨基安替吡啉和三氧化二铕为原料合成了Eu(PPA)3Phen和Eu(APA)3Phen.使用核磁和质谱对配体和配合物进行了表征,研究了紫外、荧光光谱、磷光寿命、热稳定性和电化学性质.结果表明,配合物的紫外吸收分别表现出生成它们各自配体的紫外吸收特征,Eu(PPA)3Phen和Eu(APA)3Phen在613nm处有很强的荧光发射,归属于Eu3+的5D0→7F2的特征发射,此外,在590nm处都有荧光发射.测得两种配合物粉末的磷光寿命,它们相差较大,Eu(PPA)3Phen有三个磷光寿命都约为0.0.45μs,Eu(APA)3Phen有两个磷光寿命都为650μs.热重分析表明,Eu(PPA)3Phen在30℃～260℃分解大约10%,而Eu(APA)3Phen在70℃～240℃分解大约5%.使用循环伏安法研究了Eu(PPA)3Phen和Eu(APA)3Phen的电化学性质,结果表明两者都约在0.86V处有不可逆的氧化电位值.     

Studies on synthesis and fluorescent property of rare earth complexes RE（ABMF）2AA and copolymers RE（ABMF）2AA-co-MMA

Four new complexes RE(ABMF)2AA (RE=Sm, Eu, Tb, Dy) were synthesized by the reaction of RECl3·6H2O with acrylic acid (HAA) and 1-(2-furyl)-3-phenyl-1,3-propanedione (ABMF). The copolymerization of the rare earth complexes with methyl methacrylate was studied by using 2,2-azobis-isobutyronitrile as an initiator. The composition and structure of the four complexes were characterized by elemental analysis, UV-vis and FTIR. The glass transition temperature and molecular weight of the copolymers were determined. Photoluminescent measurement showed that ligand ABMF could efficiently transfer the energy to Sm3+ and Eu3+ ions in the complexes and sensitize the luminescence of the rare earth ions, but could not sensitize Tb3+ and Dy3+ ions. As a result, both Sm3+ and Eu3+ complexes emitted the characteristic fluorescence of Sm3+ and Eu3+ ions due to the f-f transitions. The four copolymers could emit strong fluorescence of the rare earth ions.