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  

Synthesis,Mechanism and Magnetic Resonance of New Lanthanide Complexes with Noncyclic Polyether - Acetylacetone Schiff Base

作　　者：姚克敏[1] 吴静[1] 陈德余[1] 沈联芳[2] 袁汉珍[2] 

机构地区：[1]浙江大学化学系,杭州310027 [2]中国科学院武汉物理与数学所波谱与原子分子物理国家重点实验室,武汉430071

出　　处：《化学学报》1998年第9期900-904,共5页Acta Chimica Sinica

基　　金：国家自然科学基金(29671026);浙江省自然科学基金;中科院波谱与原子分子物理国家重点实验室资助课题

摘　　要：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.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 firsttime.They can be formulated as: [Ln(ACACDA)2(NO3)](NO3)2·4H2O(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 13C 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 Gd3+ in the complex have been discussed.

关 键 词：稀土配合物 直链醚 二酮 烯胺式 ACACDA 席夫碱 

分 类 号：O614.33[理学—无机化学]