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。     

铕和镧与吡啶—2,6—二甲酸配合物的NMR研究

合成了稀土铕，镧与吡啶－２，６－二甲酸形成的二元配合物及铕与邻菲罗啉和吡啶－２，６－二甲酸形成的三元配合物，经元素分析确定该配合物的组成分别为二元：Ｎａ３「Ｅｕ（ＤＰＣ）３」．２Ｈ２Ｏ，Ｎａ３「Ｌａ（ＤＰＣ）３」２Ｈ２Ｏ；三元：ＮａＥｕ（ＤＰＣ）２；ｐｈｅｎ．４Ｈ２Ｏ。用核磁共振研究了配体与稀土的配位方式，讨论了诱导效应、屏蔽效应及稀土离子的顺磁性对配合物化学位移和ＮＭＲ谱图的影响。     

铕和镧与吡啶－2，6－二甲酸配合物的NMR研究

合成了稀土铕、镧与吡啶－２，６二甲酸形成的二元配合物及铕与邻菲罗啉和吡啶－２，６二甲酸形成的三元配合物。经元素分析确定该配合物的组成分别为二元：Ｎａ３［Ｅｕ（ＤＰＣ）３］·２Ｈ２Ｏ，Ｎａ３［Ｌａ（ＤＰＣ）３］·２Ｈ２Ｏ；三元：ＮａＥｕ（ＤＰＣ）２·ｐｈｅｎ·４Ｈ２Ｏ。用核磁共振研究了配体与稀土的配位方式，讨论了诱导效应、屏蔽效应及稀土离子的顺磁性对配合物化学位移和ＮＭＲ谱图的影响。ＮＭＲ研究表明，三种配合物具有相似的对称结构和相同的化学位移变化规律。吡啶－２，６二甲酸中的羧酸以单齿配位（整个分子为三齿配位），二元配合物中，铕和镧的配位数均为９，三元配合物中，铕的配位数最低为８。     

1-(2-羟基苯基)-3-苯基-1,3-丙二酮及其铕(Ⅲ)配合物的合成和发光研究

以邻羟基苯乙酮和苯甲酰氯为原料, 经过酯化反应、 Fries重排合成了1-（2-羟基苯基）-3-苯基-1,3-丙二酮（HPPPD）及其与铕（Ⅲ）的配合物, 并通过IR, 热重-差热分析和^1H-NMR谱对其进行了表征. 研究了酚羟基的引入对稀土配合物发光性能的影响. 结果表明该配体与铕（Ⅲ）形成的配合物发出很强的铕（Ⅲ）的特征荧光, 并且以邻菲罗啉为第二配体的三元配合物的荧光强度明显高于二元配合物. 但是, 配体HPPPD与铽（Ⅲ）、钐（Ⅲ）和镝（Ⅲ）等形成的配合物, 无论是二元的, 还是三元的发光均很弱. 这是由于该配体的能级与不同稀土离子能级匹配程度的差别所致.     

桂皮酸邻菲罗啉稀土配合物的合成及表征

合成了 13种桂皮酸和邻菲罗啉为配体的稀土配合物RE(phen)L3(L =C6H5CH =CHCOO- )。研究了配合物的红外光谱、摩尔电导、热重 差热曲线、X射线粉末衍射及荧光光谱。结果表明 ,稀土离子与配体间形成了化学键 ,配合物为晶体化合物 ,在 4 0 0和 540℃氧化分解 ;铕配合物Eu(phen)L3发出较强荧光 ,而其它配合物则发光较弱。     

邻菲罗啉聚西佛碱金属配合物的合成及磁性能研究

以5,6-二胺-1,10-菲罗啉与2,6-吡啶二甲酸缩聚合成得到一种新的含邻菲罗啉结构的聚西佛碱,并制备了其相应的与过渡金属离子Ni2+和Fe2+以及稀土离子Nd3+的配合物,通过红外光谱,核磁共振和元素分析等手段对聚合物及其金属配合物的结构进行了表征,并分析和讨论了它们的磁学性能.结果表明,这一类金属配合物在低温区,...     

稀土苯二甲酸配合物的发光性能和分子内能量传递(英文)

合成和表征了一系列稀土（钆，铕，铽）的邻（间）苯二甲酸配合物．通过测定了苯二甲酸配体的钆配合物的低温磷光光谱确定其相应苯二甲酸配体的最低三重态能级．同时详细讨论了配合物的发光性能，能级匹配和分子内能量传递机制．     

新型β-二酮铕配合物的合成和性能研究

以肉桂酸和苯乙酮为原料合成了1,5-二苯基-4-烯-1,3-戊二酮（DPPD）配体,以DPPD为第一配体,1,10-邻菲罗啉为第二配体,合成了稀土铕配合物并通过红外光谱进行了表征,同时,研究了配合物的发光性能。     

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.     

高氯酸铕、铽-二苯亚砜-1，10菲咯啉配合物的合成及荧光性质研究

同时合成了高氯酸铕、铽.二苯亚砜-1,10菲咯啉三元配合物和高氯酸铕、铽-1,10菲咯啉二元配合物。以配合物进行了元素分析,摩尔电导。确定了配合物的组成分别为:[RE(DPSO)](phen)3(ClO4)2)ClO4·nH2O(n=1,3,DPSO为二苯亚砜,phen为1,10菲咯啉)和RE(phen)4(ClO4)3。红外光谱研究表明:DP-SO以氧原子与稀土离子配位;phen以氮原子与稀土离子配位;三元配合物中ClO4-中两个与稀土离子配位,二元配合物中三个ClO4-均与稀土离子配位。对比研究了两类配合物的发光性能,溶解性能及稳定性能。研究结果表明:第二配体DPSO的加入,大大改善了配合物的发光性能,可分别使铕、铽的发光强度提高2和8倍。同时大大改善了配合物的溶解性能及稳定性能。     

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。     

Synthesis and cofluorescence of Eu(Y) complexes with salicylic acid and o-phenanthroline

A series of dinuclear complexes of salicylic acid (HSal) and o-phenanthroline (Phen) with different molar ratios of Eu3+ to Y3+ have been synthesized. Their compositions are Eu(x)Y(1-x) (Sal)3(Phen) (x = 0 to approximately 1). Their UV spectra, IR spectra, and fluorescence spectra were studied. The UV spectra of the complexes reflect essentially absorption of the ligands for the fact that no obvious change of wavelength and band shape is found between the spectra of the complexes and that of the ligands except slight red shift. The IR absorption spectra indicate that salicylic acid is coordinated to the rare earth ions and chemical bonds are formed between rare earth ions and nitrogen atoms of o-phenanthroline. The fluorescence spectra of the complexes indicate that the fluorescence emission intensity of europium ion was enhanced by the addition of Y3+, which is referred to as cofluorescence. These facts show that not only the ligands but also the yttrium complex can transfer the absorbed energy to Eu3+ ion in the complexes. Formation of polynuclear complexes appears to be responsible for cofluorescence.     

Synthesis, characterization and luminescent properties of new highly luminescent organic ligand and complexes of trivalent rare earth

A novel ligand with two carboxylic groups has been synthesized. The composition and structure of the ligand were characterized by IR, (1)H NMR and MS spectrometry. The highly luminescent intensity complexes were prepared with the ligand and phen. The IR, solid state (13)C NMR and fluorescent spectra of the complex were studied. IR absorption spectra indicate that the ligand is coordinated to the Eu(3+) ion, and chemical bonds are formed between Eu(3+) ion and nitrogen atoms of phen. The fluorescent spectra illustrate that the complex has an excellent luminescence, indicating the ligand favors energy transfer to the emitting energy level of Eu(3+). The influences of pH and reaction solvent on the fluorescence intensity of the complex were also discussed.     

5-氯-2-甲氧基苯甲酸与1,10-邻菲啰啉稀土配合物的合成、表征及热分解机理

合成了三种稀土配合物[Ln(5-Cl-2-MOBA)3phen]2(Ln=Nd(1),Eu(2),Ho(3);5-Cl-2-MOBA:5-氯-2-甲氧基苯甲酸根;phen:1,10-邻菲啰啉),通过元素分析、热重-微分热重-差示扫描量热(TG-DTG-DSC)、红外光谱(IR)、紫外光谱(UV)及摩尔电导等技术对标题配合物进行了表征.荧光光谱表明配合物(2)发出铕离子的特征荧光.用热分析/傅里叶变换红外(TG-DSC/FTIR)联用技术,阐明标题配合物的热分解反应机理,并分析了逸出气体的三维(3D)红外光谱.     

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。     

新型铕,铽(Ⅲ)三元配合物的合成、表征及发光性能

采用Claisen缩合反应设计合成了β-二酮配体1-(4-溴苯)-4,4,4-三氟丁烷-1,3-二酮(BPT),并合成了相应的新型稀土Eu,Tb(Ⅲ)三元配合物。通过元素分析、1H NMR谱、红外光谱、紫外光谱、荧光光谱和磷光光谱技术对合成的产物进行了表征和分析。红外光谱分析表明:BPT中存在着酮式-烯醇式互变;配合物中的稀土离子与BPT中的氧原子以及Phen中的氮原子形成了配位键。紫外光谱表明配合物主要是由第一配体BPT吸收能量。荧光光谱显示Eu(BPT)3Phen的发光强度较大,进一步的研究表明,BPT的最低三重态能级与Eu3+的5D0能级匹配较好。     

Synthesis and fluorescence properties of rare earth (Eu3+ and Gd3+) complexes with alpha-naphthylacetic acid and 1,10-phenanthroline

Rare earth binary complex Eu(NNA)3 (NNA, alpha-naphthylacetic acid), ternary complex Eu(NNA)3.phen (phen, 1,10-phenanthroline) and a series of dinuclear complexes with different mole ratios of Eu3+ to Gd3+ were synthesized. Many advanced approaches, such as element analysis, FTIR spectra, TG and DTA analysis, were used to determine the composition and structure of binary and ternary complex. Moreover, their fluorescence properties were studied by fluorescent spectra and lifetimes. The fluorescence spectra and decay curves of dinuclear complexes indicated that the fluorescence emission intensity was enhanced and the fluorescence lifetime was prolonged by Gd3+. The dinuclear complexes show the best properties when the mole ratio of Eu3+ to Gd3+ is 6:4. A new parameter Y, which was used to evaluate the effect of Gd3+, was introduced. In addition, the relationship of Y value and mole fraction of Gd3+ was analyzed by mathematical software. The results showed that Y value decreased by single exponential mode when the content of Gd3+ decreased.     

Synthesis and infrared and fluorescence spectra of new europium and terbium polynuclear complexes with an amide-based 1,10-phenanthroline derivative

An amide-based 1,10-phenanthroline (phen) derivative and its complexes with europium(III) and terbium(III) ions were synthesized. The complexes were characterized by elemental analysis, infrared spectra and conductivity. The europium and terbium ions were coordinated by O atoms of C=O, Ar-O-C and N atoms of phen. The fluorescence properties of the complexes in THF, dioxane, MeCN and DMF were investigated. Under the excitation of UV light, these complexes exhibited characteristic fluorescence of europium and terbium ions. The solvent factors influencing the fluorescent intensity were discussed.     

Synthesis, infrared and fluorescence spectra of lanthanide complexes with a new amide-based 1,3,4-oxadiazole derivative

A new amide-based 1,3,4-oxadiazole derivative ligand 2,5-bis[2-(N,N-diethyl-1'-oxopropylamide)phenyl]-1,3,4-oxadiazole (L) and its complexes, Ln(NO3)3L (Ln=La, Eu, Gd, Tb, Er), were synthesized. The complexes were characterized by elemental analysis, infrared spectra and conductivity. The lanthanide ions were coordinated by O atoms from CO. The fluorescence properties of Eu(NO3)3L and Tb(NO3)3L in the solid state and in different solvents were investigated. Under the excitation of UV light, these complexes exhibit characteristic fluorescence of europium and terbium ions. The solvent factors influencing the fluorescent intensity were discussed.