【作者】 张霞；

【导师】 朱保华；

【作者基本信息】 内蒙古大学 ， 化学， 2016， 硕士

【摘要】 三联吡啶类衍生物配位稀土发光配合物因其荧光性能较为优良而受到广泛关注。为丰富三联吡啶类衍生物配位稀土发光配合物的种类,构筑光致发光性能优良的稀土发光配合物,本文参考文献方法合成了3个已知的三联吡啶衍生物1,3-二([2,2’：6’,2"-三吡啶]-4’-基)苯(L1)；1,4-二([2,2’：6’,2"-三吡啶]-4’-基)苯(L2)；三溴化1,3,5-三{[4’-(2,2’：6’2"-三吡啶基)-1-吡啶鎓基]亚甲基}苯(L3),并进一步与稀土硝酸盐反应,得到三个系列14个新的双核稀土配合物和7个新的三核稀土配合物。利用红外光谱、核磁、质谱、热重、元素分析对以上的配合物的结构进行了表征,并通过紫外-可见吸收光谱、荧光光谱和磷光光谱对它们的光学性质进行了研究,还从配体的结构上对其发光的差异性进行了解释。此外,还用L2与Zn(NO3)2和Tb(NO3)3在水热条件下自组装反应得到1个新的四核过渡金属Zn化合物的单晶,利用X-射线单晶衍射分析对其结构进行了表征。具体工作如下：首先,利用配体L1、L2分别与稀土硝酸盐Ln(NO3)3xH2O在氩气保护下以物质的量比为1：2进行投料,最终得到14个双核稀土配合物[Ln2(Li)(NO3)6·xH2O] (Ln=Eu 1a, Tb 1b, Sm 1c, Dy 1d, Nd 1e, Yb 1f, Er 1g), [Ln2(L2)(NO3)6·xH2O] (Ln=Eu 2a, Tb 2b, Sm 2c, Dy 2d, Nd 2e, Yb 2f, Er 2g)。荧光光谱研究表明,配体L1和L2不仅能够较好地敏化Eu3+、Tb3+、Sm3+、Dy3+在可见光区的特征发光,还可以敏化Nd3+、Yb3+在近红外区的特征发光,但是不能敏化Er3+在近红外区的特征发光。其次,利用配体L3分别与硝酸稀土盐Ln(NO3)3·xH2O以物质的量之比为1：3投料反应,得到7个三核稀土配合物[Ln3(L3)(NO3)9·xH2O] (Ln=Eu 3a, Tb 3b, Sm 3c, Dy 3d, Nd 3e, Yb 3f, Er 3g)。荧光光谱研究表明,配体L3能够有效地敏化Sm3+、Eu3+、Tb3+、Dy3+在可见光区的特征发光,还可以敏化Nd3+、Yb3+在近红外区的特征发光,但是不能敏化Er3+在近红外区的特征发光。最后,在液氮低温条件下测定了Gd2-L1、Gd2-L2、Gd3-L3配合物的磷光光谱,为配体L1、L2、L3的传能提供了理论依据。还从配合物的结构特点对其能量转移效率的影响考虑,对三个系列稀土发光配合物的荧光寿命和荧光量子产率进行了分析,同时还与文献中的类似配体合成的配合物进行了比较,得出的结论与文献一致。值得一提的是,配合物Eu2-L2和Tb3-L3的荧光寿命达1.104毫秒和1.019毫秒,配合物Eu2-L2的荧光量子产率为26.97%,表明该配合物在光致发光材料领域具有潜在应用价值。更多还原

【Abstract】 As a result of their excellent luminescent properties, the rare earth luminescent complexes containing the terpyridine ligand have aroused widelyattention. In order to diversify the species of the lanthanide luminescent complexes and to construct rare earth coordination complexes with unique photophysical properties, two known compounds ofl,3-di([2,2’:6’,2"-terpyridin]-4’-yl)benzene (Li) and 1,4-di([2,2’:6’,2"-terpyridin]-4’-yl)benzene(L2) and tribromide 1,3,5-tris{[4’-(2,2’:6’2"-terpyridine-yl)-1-pyridinium-yl] methylene} benzene(L3) were synthesized. Further,14binuclear and 7 three nuclear new lanthanide luminescent complexes were obtained by reactions of the three ligands (L1, L2, L3) with the rare earth nitrate salts, respectively. All of them were characterized by IR,1HNMR, MS, thermal gravimetric analysis and elemental analysis. The luminescent properties of these complexes were also investigated by UV-vis, fluorescence spectroscopyand phosphorescence spectrum. In addition, a new fournuclear metal compound based onL2 were accidentally obtained by reaction of L2 withTb(NO3)3 and Zn(NO3)2using hydrothermal method, and its crystal structure was determined by single-crystal X-ray diffraction analysis.First of all,14binuclear lanthanide complexes [Ln2(L1)(NO3)6·xH2O] (Ln=Eu 1a, Tb 1b, Sm 1c, Dy 1d, Nd 1e, Yb 1f, Er 1g), [Ln2(L2)(NO3)6·xH2O] (Ln=Eu 2a, Tb 2b, Sm 2c, Dy 2d, Nd 2e, Yb 2f, Er 2g)were obtained by reactions of L1,L2 with Ln(NO3)3·xH2O under the ratio of 1:2. The fluorescence spectroscopies of these complexes reveal that L1 and L2 can sensitize the luminescence of Eu3+,Tb3+,Sm3+ Dy3+ inthe visible regionand Nd3+ and Yb3+ inthe NIR region.Furthermore, the reactions of tridentate L3 with Ln(NO3)3·xH2O at a ratio of 1:3, afforded 7three nuclear complexes[Ln3(L3)(NOs)9·xH2O] (Ln=Eu 3a, Tb 3b, Sm 3c, Dy 3d, Nd 3e, Yb 3f, Er 3g). The fluorescence spectroscopies of the complexes demonstrate that L3 can sensitize the luminescence of Sm3+,Eu3+,Tb3+,Dy3+ inthe visible regionand Nd3+ and Yb3+ inthe NIR region.Finally, The phosphorescence spectrum of Gd2-L1,Gd2-L2,Gd3-L3 complexes provide the theoretical basis on the energy transfer of the ligand L1,L2,L3.The discussion on the luminescent intensity, fluorescent lifetime and quantum yields of the three different series compounds were carried out from the viewpoint of structure characteristics of L1-L3 and their energy transfer efficiency. It is worth mentioning that the compounds Eu2-L2 and Tb3-L3 show long fluorescent lifetime about 1.104 milliseconds and 1.019 milliseconds,and the quantum yields of the compound Eu2-L2 reaches 26.97%, which have potential application value on the photo-luminescent materials.更多还原