卤代苯甲酸铽与1,10-邻菲哕啉三元配合物的合成及性质

以卤代苯甲酸和1,10-邻菲哕啉为配体,合成了9种Tb(Ⅲ)的三元配合物,以EDTA配位滴定分析和元素分析确定了各配合物的组成。通过红外光谱分析对配合物的结构进行了初步表征,在配合物中羧基氧原子和1,10-邻菲啰啉中的氮原子均参与了配位。采用TG-DTG技术对配合物的热稳定性进行了研究,9种配合物均有较好的热稳定性,它们的热稳定性顺序为:Tb(o-ClBA)₃phen>Tb(o-BrBA)₃phen>Tb(p-ClBA)₃phen>Tb(m-BrBA)₃phen·H₂O>Tb(o-FBA)₃phen>Tb(p-BrBA)₃phen>Tb(p-FBA)₃phen>Tb(m-ClBA)₃phen≈Tb(m-FBA)₃phen·H₂O。在同一条件下测得了各配合物固体粉末的激发和发射光谱,结果表明:相同取代基和相同取代位置的各组配合物的两个较强发射峰(⁵D₄-⁷F₆和⁵D₄-⁷F₅)的荧光强度顺序分别为:Tb(o-FBA)₃phen>Tb(p-FBA)₃phen>Tb(m-FBA)₃phen·H₂O,Tb(m-ClBA)₃phen>Tb(p-ClBA)₃phen>Tb (o-ClBA)₃phen,Tb(p-BrBA)₃phen>Tb(o-BrBA)₃phen>Tb(m-BrBA)₃phen·H₂O和Tb(o-FBA)₃phen>Tb (o-BrBA)₃phen>Tb(o-ClBA)₃phen,Tb(m-ClBA)₃phen>Tb(m-FBA)₃phen·H₂O>Tb(m-BrBA)₃phen·H₂O,Tb(p-BrBA)₃phen>Tb(p-ClBA)₃phen>Tb(p-FBA)₃phen[其中o(m,p)-F(Cl,Br)BA为邻(间,对)氟(氯,溴)苯甲酸根,phen为1,10-邻菲哕啉]。

Synthesis and Properties of Ternary Terbium Complexes with Halogen-benzoic Acid and 1, 10-phenanthroline

The rare-earth carboxylate complexes are a kind of good luminous materials.With the tremendous progress of OEL,the research of rare-earth carboxylate complexes as electroluminescent device emitting layer material is increasing.The application prospects of these complexes become more and more broad.Tb (Ⅲ) earboxylate complexes are a kind of good green luminescence material.In our previous work,we found that some neutral conjugated heterocyclic ligands (such as phen or bipy) can enhance the luminescent intensity to some extent in Tb (Ⅲ) aromatic carboxylate compounds.In these studies about rare-earth aromatic carboxylate complexes,a lot of researches about the complexes of terbium with carboxylate have been reported,but the study of terbium complexes with halogen-benzoic acids as the first ligand is seldom reported.In order to compare the properties of the complexes in series,nine ternary complexes of rare-earth halogen-benzoic acids with 1,10-phenanthroline were synthesized in this paper.These complexes were characterized by elemental analysis,IR and TG-DTG methods.In these complexes,the Tb (Ⅲ) ions are bonded to the oxygen atoms of carboxylate and the nitrogen atoms of phen.The TG-DTG analysis showed that these complexes are thermally stable.The stability order of the complexes is:Tb (o-CIBA)₃ phen>Tb (o-BrBA)₃ phen>Tb (p-CIBA)₃ phen>Tb(m-BrBA)₃phen·H₂O>Tb(o-FBA)3phen>Tb(p-BrBA)₃phen>Tb (p-FBA)₃phen>Tb (m-ClBA)₃phen≈Tb(m-FBA)₃phen·H₂O.Their excitation and luminescence spectra were performed under identical conditions and instrumental parameters at room temperature.The results indicate that the fluores-cence intensity changes with the different substituent on the benzene ring or the same substituent in different positions.The order of their fluorescence intensity is Th (o-FBA)₃phen>Th (p-FBA)₃phen>Tb (m-FBA)₃phen·H₂O,Tb(m-ClBA)₃phen>Tb(p-ClBA)₃phen>Tb(o-CIBA)₃phen,Tb(p-BrBA)₃phen>Tb (o-BrBA)₃ phen>Tb (m-BrBA)₃ phen·H₂O;Tb (o-FBA)₃ phen>Tb (o-BrBA)₃ phen>Tb (o-ClBA)₃ phen, Tb (m-ClBA)₃ phen>Tb (m-FBA)₃ phen·H₂P>Th (m-BrBA)₃ phen>H₂O,Tb (p-BrBA)₃ phen>Tb (p-ClBA)₃ phen>Th (p-FBA)₃ phen [o(m,p)-F(Cl,Br) BA:(0 (m,p)-Fluorobenzoic (Chlorobenzoic,Bromo-benzoic) acid;phen:1,10-phenanthroline].