3,4-二甲基吡咯-2-甲酰肼缩PMBP的镧系(Ce、Pr、Nd)配合物的合成、结构及荧光性质
Lanthanide Complexes (Ce, Pr, Nd) with an Acylhydrazone Derived from 3,4-Dimethylpyrrole-2-carbohydrazide and PMBP: Syntheses, Crystal structures and Fluorescence Properties
作者单位E-mail
常慧琴 河南理工大学化学化工学院, 焦作 454000  
陈亮 河南理工大学物理与电子信息学院, 焦作 454000 cl721@hpu.edu.cn 
吴伟娜 河南理工大学化学化工学院, 焦作 454000 wuwn08@hpu.edu.cn 
王元 河南理工大学化学化工学院, 焦作 454000  
摘要: 合成并通过单晶衍射表征了3个稀土配合物[LnL(NO33(H2O)][LnL(NO33(CH3CN)]·2CH3CN(Ln=Ce (1),Pr (2),Nd (3),L=3,4-二甲基吡咯-2-甲酰肼缩PMBP)。3个配合物同构,属于单斜晶系,P21/n空间群,晶胞参数分别为:1a=1.758 83(9) nm,b= 1.460 61(8) nm,c=2.626 28(14) nm,β=97.800 0(10)°;2a=1.756 39(15) nm,b=1.459 97(11) nm,c=2.623 1(2) nm,β=97.771(2)°;3a=1.758 7(2) nm,b=1.463 87(17) nm,c=2.626 3(3) nm,β=97.760(2)°。每个配合物包含2个不同的中性配合物分子。配合物中每个十配位的Ln(Ⅲ)离子与来自酰腙配体L的2个氧原子和1个氮原子,3个双齿配位硝酸根及1个溶剂分子配位,采取双帽四方反棱柱配位构型。乙腈溶液中,配合物1~3具有与配体完全不同的荧光发射,可能由配位荧光增强效应导致。
关键词: 吡咯  酰腙  稀土配合物  荧光  晶体结构
基金项目: 国家自然科学基金(No.21001040)和河南省教育厅自然科学基金(No.12B150011,14B150029)资助项目。
Abstract: Three lanthanide(Ⅲ) complexes, [LnL(NO3)3(H2O)][LnL(NO3)3(CH3CN)]·2CH3CN (Ln=Ce (1), Pr (2) and Nd (3)) based on L (L is derived from 3,4-dimethylpyrrole-2-carbohydrazide and PMBP) have been synthesized and characterized by elemental analyses, IR spectra and X-ray diffraction analyses. The results reveal that three complexes are isostructural and crystallize in the monoclinic, space group P21/n (a=1.758 83(9) nm, b=1.460 61(8) nm, c=2.626 28(14) nm, β=97.800 0(10)° for 1; a=1.756 39(15) nm, b=1.459 97(11) nm, c=2.623 1(2) nm, β=97.771(2)° for 2; a=1.758 7(2) nm, b=1.463 87(17) nm, c=2.626 3(3) nm, β=97.760(2)° for 3). Each of them contains two kinds of independent neutral complex molecules. Concomitantly, each Ln(Ⅲ) ion is surrounded by one tridentate ligand L with NO2 donor set, three bidentate nitrate anions and one coordination solvent molecule, thus giving a bicapped square antiprism coordination geometry. In addition, in CH3CN solution, complexes 1~3 exhibit different fluorescence emission from that of the ligand L probably due to a CHEF (chelation enhancement of the fluorescence emission) effect.
Keywords: pyrrole  hydrazone  lanthanide complex  fluorescence  crystal structure
投稿时间:2015-12-18 修订日期:2016-04-19
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常慧琴,陈亮,吴伟娜,王元.3,4-二甲基吡咯-2-甲酰肼缩PMBP的镧系(Ce、Pr、Nd)配合物的合成、结构及荧光性质[J].无机化学学报,2016,32(7):1239-1245.
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