【作者】 石晓燕；

【导师】 李文先；

【作者基本信息】 内蒙古大学 ， 无机化学， 2009， 硕士

【摘要】 以二苯甲酰基甲基亚砜（L=C₆H₅COCH₂SOCH₂COC₆H₅）为第一配体,分别以邻菲啰啉、苯甲酸、水杨酸、联吡啶为第二配体（L’）与高氯酸稀土合成了四个系列十六种固态配合物。经元素分析、稀土络合滴定、摩尔电导率及热重-差示扫描量热分析,表明配合物的组成为:RE（L）₅ L’（ClO₄）₃·2H₂O（RE=Sm,Eu,Tb,Dy;L’=邻菲啰啉,联吡啶）; Sm（L）₅ L’（ClO₄）₂·7H₂O（L’=C₆H₅COO^-,C₆H₄OHCOO^-）; Eu（L）₅L’（ClO₄）₂·8H₂O（L’=C₆H₅COO^-）; Eu（L）₅L’（ClO₄）₂·6H₂O（L’=C₆H₄OHCOO^-）;Tb（L）₅ L’（ClO₄）2·6H₂O（L’=C₆H₅COO^-,C₆H₄OHCOO^-）;Dy（L）₅L’（ClO₄）₂·8H₂O（L’=C₆H₅COO^-,C₆H₄OHCOO^-）。红外光谱、核磁共振氢谱表明,亚砜配体通过一个亚砜基氧原子与稀土离子配位,羰基未参与配位,而邻菲啰啉和联吡啶通过各自的两个氮原子与稀土离子配位,苯甲酸通过羧基以单齿形式与稀土离子配位,水杨酸通过羧基以单齿形式与稀土离子配位,同时酚羟基中的氧原子也参与了配位。配合物在DMF溶液中测定的摩尔电导率表明,亚砜邻菲啰啉类以及亚砜联吡啶类稀土三元配合物为1:3型,三个ClO₄^-无机抗衡阴离子全部在外界未参与配位;而亚砜苯甲酸类以及亚砜水杨酸类稀土三元配合物为1:2型,两个ClO₄^-无机抗衡阴离子也全部在外界未参与配位。配合物的荧光光谱表明,钐、铕、铽、镝各稀土三元配合物均产生了特征荧光发射光谱。各类稀土三元配合物的荧光强度与二元配合物相比,有的增强,但有的却是减弱的。根据磷光光谱,这主要是因为在各类稀土三元配合物当中,第二配体邻菲啰啉、苯甲酸、水杨酸、联吡啶三重态能级的范围以及能级的高低不同,使得亚砜配体以及第二配体在紫外区吸收能量之后,能量传递的效率以及能量传递的难易程度明显不同造成的。配合物的荧光衰减曲线表明,钐、铕、铽、镝各稀土三元配合物均具有较强的荧光寿命。更多还原

【Abstract】 Sixteen solid trinary complexes of rare earth perchlorate with bis（benzoylmethyl） sulfoxide （L） as the first ligand and O-Phenanthroline（L’）, Benzoic Acid（L’）, Salicylic Acid（L’）, 2.2’ -Dipyridyl（L’） as the second ligands have been synthesized and characterized. By elemental analysis, coordination titration and TGA-DSC studies, the composition of the complexes were suggested as RE （L）₅ L’（ClO₄）₃·2H_O （RE=Sm,Eu,Tb,Dy;L’=O-Phenanthroline,2.2’-Dipyridyl）;Sm（L）₅L’（ClO₄）₂·7H₂O（L’=C₆H₅COO^-,C₆H₄OHCOO^-）;Eu（L）₅L’（ClO₄）₂·8H₂O（L’=C₆H₅COO^-）;Eu（L）₅L’（ClO₄）₂·6H₂O（L’=C₆H₄OHCOO^-）; Tb （L）₅ L’（ClO₄）₂·6H₂O （L’=C₆H₅COO^-,C₆H₄OHCOO^-）; Dy （L）₅ L’ （ClO₄）₂·8H₂O （L’=C₆H₅COO^-, C₆H₄OHCOO^-）. IR spectra and ¹HNMR spectra studies indicated that bis（benzoylmethyl） sulfoxide （L） bonded with RE³⁺ ions by the oxygen atom in sulfinyl group while the oxygen atom in carbonyl group did not. The second ligands O-Phenanthroline and 2.2’ -Dipyridyl bonded with RE³⁺ ions by the nitrogen atom respectively. The second ligand Benzoic Acid bonded with RE³⁺ ions by one oxygen atom in carbonyl group which coordinated as an unidentate group. But the second ligand Salicylic Acid not only bonded with RE³⁺ ions by one oxygen atom in carbonyl group which coordinated as an unidentate group but also bonded with RE³⁺ ions by one oxygen atom in the phenolic hydroxyl group. The molar conductivities in DMF solution indicated that all the inorganic anions ClO₄^- are not coordinated with RE³⁺. The fluorescence spectra illustrate that all of the Sm³⁺, Eu³⁺, Tb³⁺ and Dy³⁺ complexes display characteristic metal-centered fluorescence in solid state. As phosphorescent spectra of ligands show that the triplet state of second ligands have different energy level and different scope., the efficiency of the energy transfer is different. So compared with the binary complexes, some trinary complexes have stronger fluorescence but the others do not. The fluorescence decay curves illustrate that all the complexes have long fluorescence lifetime.更多还原