【作者】 张燕广；

【导师】 魏丹毅； 谢洪珍；

【作者基本信息】 宁波大学 ， 物理化学， 2011， 硕士

【摘要】 本文第一部分对1,10-邻菲啰啉、联吡啶类为第一配体，芳香羧酸类为第二配体的配合物的晶体结构进行了综述。报道了一系列含氮芳环/芳香羧酸稀土配合物的合成方法,9种新型配合物、1种有机化合物的晶体结构,并对相应的配合物进行了红外光谱、差热-热重、X-射线粉末衍射表征和荧光光谱的分析。最后研究了两种稀土配合物对几种阴离子的识别性能。稀土硝酸盐、2,2’:6’,2’’-三联吡啶（tpy）、2,2’–联苯二甲酸（dpdc）在水热反应条件下得到了三种结构新颖的稀土金属配合物[Er（dpdc）₂(tpy]_n（1）、[Ln₂（dpdc）₄（tpy）₂]_n·H₂O [Ln=Nd（2）、Yb（3）]。属于三斜晶系的配合物Er（dpdc）₂（tpy）]_n是具有对称中心的双核结构,每个结构单元中含有两个Er³⁺离子、四个2,2’-联苯二甲酸根离子和两个2,2’:6’,2’’--三联吡啶分子,而属于单斜晶系异质同晶型配合物[Ln₂（dpdc）₄（tpy）₂]_n·H₂O （Ln= Nd、Yb）是由一个稀土Ln³⁺离子、一个螯合的2,2’:6’,2’’-三联吡啶分子、两个2,2’-联苯二甲酸根离子组成。2,2’-联苯二甲酸羧根桥联配合物形成了一种无限延伸的一维链结构。稀土硝酸盐、2,2’:6’,2’’-三联吡啶、2,2’–联苯二甲酸和乙酸通过溶液法得到异质同晶配合物[Ln₂（dpdc）₂（tpy）₂ （M）₂（H₂O）₂]·H₂O （Ln=La（4）、Yb（5）、Pr（6）、Gd（7）和Sm（8）,M=乙酸）,这五种配合物的共同特征是都为双核结构,中心离子Ln³⁺分别与来自于2,2’-联苯二甲酸、乙酸、配位水分子中的七个氧原子和2,2’:6’,2’’-三联吡啶的三个氮原子配位,形成了双帽四方反棱柱体结构。配体2,2’-联苯二甲酸的两个羧基采用了两种不同的配位方式和稀土金属离子配位,一种是羧基上的两个氧原子同时与金属离子螯合配位,另一种是羧基上的一个氧原子与另一个金属离子单齿配位。稀土Tb³⁺（Ⅲ）、2,2’-二联吡啶（bpy）和3-甲基-2-硝基苯甲酸（L）以乙醇作为溶剂采用溶液法得到一个稀土配合物[Tb（bpy）₃L]·2H₂O（9）,该配合物是一个中心对称的双核分子,每个Tb³⁺与五个3-甲基-2-硝基苯甲酸根离子的七个O原子和2,2’-联吡啶分子的两个N原子配位,形成了九配位的扭曲的三帽四方反棱柱结构,多面体之间通过公用边得到Tb₂N₄O₁₂二聚体。荧光光谱显示,这两个芳环配体能够较好的增强铽离子的荧光效应。以稀土配合物Eu（phen）₂（NO₃）₃、Tb（phen）₂（NO₃）₃为荧光化学传感器的阴离子识别性能研究结果表明:F-离子能使配合物荧光发生猝灭;随着HSO₄^-离子浓度的增大,配合物荧光强度先增强后减弱;NO₃^-、Ac^-、Cl^-、Br^-和I^-离子的加入对配合物的发光性能几乎没有影响。更多还原

【Abstract】 The crystal structures of rare earth complexes with phen/bipy ligand were reviewed. The syntheses, crystal structures of nine new coordination complexes and one organic compound were reported. At the same time, they were characterized by IR spectroscopically, thermogravimetric analysis, X-ray powder diffraction and the luminescent properties. Finally, the anion recognition properties of two lanthanide complexes were investigated.Hydrothermal reactions of Ln（NO）₃, 2,2’:6’,2’’-Terpyridine（tpy） and 2,2`-dpdc afforded [Er （dpdc）<sub>2</sub>（tpy）]n（1）、[Ln<sub>2</sub>（dpdc）<sub>4</sub>（tpy）<sub>2</sub>]n·H<sub>2</sub>O (Ln= Nd（2）、Yb（3）]. In the centrasymmetric binuclear complex [Er（dpdc）<sub>2</sub>（tpy）<sub>2</sub>]n, each asymmetric unit contains two Er<sup>3+</sup>, four 2,2`-dpdc ,one chelate tpy molecule. The complexes 2-3 crystallize isostructurally in a monoclinic system and they consist of one Ln³⁺ ions, one chelate L and two 2,2`-dpdc. The Ln<sup>3+</sup> are bridged by 2,2`-dpdc ligand to generate 1D chain.The five rare earth complexes [Ln₂（dpdc）₂（tpy）（M）₂（H₂O）]n. H₂O [ Ln=La（4）、Yb（5）、Pr（6）、Gd（7） and Sm（8）; M=Acetic acid] were obtained by the solution reaction of lanthanide ion, tpy, 2,2`-dpdc and acetic acid. In these complexes, each Ln<sup>3+</sup> is coordinated by seven oxygen atoms and three nitrogen atoms from tpy to form a distorted square antiprism geometry.The complex was synthesized by reaction of Tb<sup>3+</sup>, 2,2’,-Bipyridine（bpy）, L（L=3-Methyl-2-nitrobenzoic acid） in ethanol solution. In each centrasymmetric binuclear complex [Tb（bpy）<sub>3</sub>L]·2H<sub>2</sub>O（9）, Tb atom is coordinated by seven oxygen atoms, from five M and two nitrogen atom from one bpy. The 9-coordinated Tb atoms exhibiting tri-copped trigonal prismatic geometry formed Tb<sub>2</sub>N<sub>4</sub>N<sub>12</sub> dimer by edge shared. The fluorescence emission spectra show that the two aromatic ring ligands can increase the luminescence. In the complex, 2,2`-bpy has two different coordination modes. One mode is 2,2`-bpy chelate one Ln³⁺ with tow carboxyl oxygen atoms and the other mode is one carboxyl oxygen atoms connected the other Ln³⁺ with mono coordination.Two complexes Tb（phen）₂（NO₃）₃ and Eu（phen）₂（NO₃）₃ were synthesized. The recognition behavior of the complexes toward various anions was investigated. When fluoride anions were added into the solution of Tb（phen）₂（NO₃）₃, the fluorescence was quenched. When HSO₄^2- anions were added , fluorescence of complex were decreased gradually in fibrosis reversal. However, when the NO₃^-、Ac^-、Cl^-、Br^- and I^- anions were added , the fluorescence has no change.更多还原