化学学报 ›› 1998, Vol. 56 ›› Issue (9): 900-904. 上一篇    下一篇

研究论文

稀土与直链醚-乙酰丙酮Schiff碱新配合物合成、形成机理 与波谱

姚克敏;吴静;陈德余;沈联芳;袁汉珍   

  1. 浙江大学化学系.杭州(310027);中国科学院武汉物理与数学研究所;波谱与原 子分子物理国家重点实验室;杭州师范学院化学系
  • 发布日期:1998-09-15

Synthesis, mechanism and magnetic resonance of new lanthanide complexes with noncyclic polyether-acetylacetone Schiff base

Yao Kemin;Wu Jing;Chen Deyu;Shen Lianfang;Yuan Hanzhen   

  1. Zhejiang Univ, Dept Chem.Hangzhou(310027)
  • Published:1998-09-15

首次合成了直链醚Schiff碱,乙酰丙酮缩二甘醇二胺(ACACDA),并以分步法得到它与稀土元素的九种新配合物:[Ln(ACACDA)~2(NO~3)](NO~3)~2·4H~2O(Ln=La,Pr,Nd,Sm,Gd,Tb,Er,Yb,Y)。以紫外、红外光谱,特别是500MHz的NMR谱表征了配合物,通过其形成机理探讨,证明配合物中配体采取烯胺式构型形成稳定共轭结构。研究了Gd配合物的EPR谱,呈"U"谱特征,并出现"零场效应",据此讨论了配合物中晶体场强度及Gd^3^+周围的局部对称性。

关键词: 稀土金属络合物, 乙酰丙酮, 席夫碱, 醚, 直链, 稀土元素, 烯胺, β-双酮类, 波谱分析, 合成

Nine novel Ln(Ⅲ) complexes with Schiff base (ACACDA) derived from diethylene glycol diamine and acetylacetone have been synthesized by the "step by step" method for the first time. They can be formulated as: [Ln(ACACDA)~2(NO~3)](NO~3)~2·4H~2O (Ln=La, Pr, Nd, Sm, Gd, Tb, Er, Yb, Y). Enamic form mechanism in the ligand of the complexes was suggested and proved by UV, IR, especially ^1H and ^1^3C NMR spectra. The EPR spectrum of the Gd(Ⅲ) complex exhibits the "U" spectral feature and "zero field effect". On this basis, the crystal field strength and the local symmetry around Gd^3^+ in the complex have been discussed.

Key words: RARE EARTH METAL COMPLEX, ACETOPREPANONE, SCHIFF BASE, ETHER, STRAIGHT CHAIN, RARE ELEMENT, ENAMINES, β-DIKETONES, SPECTROMETRIC ANALYSIS, SYNTHESIS

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