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一种由半刚性三脚架羧酸配体构建的新型镧系配位聚合物:合成、晶体结构与性质

A new lanthanum coordination polymer built from a semi-rigid tripodal carboxylic acid ligand: synthesis, crystal structure and properties.

作者信息

Zhou Lian, Shi Pei Dong, Guo Xiao Kun, Feng Xiu Cun, Wang Lin Lin, Zhang Jun

机构信息

State Key Laboratory of Plateau Ecology and Agriculture, Qinghai University, Xining 810006, People's Republic of China.

School of Materials and Chemical Engineering, Anhui University of Architecture, Hefei 230601, People's Republic of China.

出版信息

Acta Crystallogr C Struct Chem. 2019 Sep 1;75(Pt 9):1280-1285. doi: 10.1107/S2053229619011240. Epub 2019 Aug 19.

Abstract

By employing the semi-rigid multidentate carboxylic acid ligand 4,4',4''-{[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(oxy)}tribenzoic acid (denoted HL), a new lanthanum coordination polymer, namely poly[[bis(dimethylformamide)(μ-4,4',4''-{[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(oxy)}tribenzoato)lanthanum(III)] dimethylformamide tetrasolvate 0.25-hydrate], {[La(CHO)(CHNO)]·4CHNO·0.25HO} or {[La(L)(DMF)]·4(DMF)·0.25(HO)} (DMF is dimethylformamide) (1), was prepared and characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, IR spectroscopy and photoluminescence studies. The asymmetric unit contains one La cation, one anionic L ligand, two coordinated DMF molecules, four free DMF molecules and one-quarter of a free water molecule. Compound 1 possesses (3,6)-connected two-dimensional kgd topology sheets consisting of secondary building units of La clusters and L ligands, which further stack into three-dimensional supramolecular networks through π-π interactions. Compound 1 exhibits a photoluminescence emission at room temperature, with a peak at 410 nm, owing to a ligand-centred excited state.

摘要

通过使用半刚性多齿羧酸配体4,4',4''-{[(2,4,6-三甲基苯-1,3,5-三基)三(亚甲基)]三(氧基)}三苯甲酸(表示为HL),制备了一种新型镧系配位聚合物,即聚[[双(二甲基甲酰胺)(μ-4,4',4''-{[(2,4,6-三甲基苯-1,3,5-三基)三(亚甲基)]三(氧基)}三苯甲酸根)镧(III)]二甲基甲酰胺四溶剂合物0.25水合物],{[La(CHO)(CHNO)]·4CHNO·0.25HO}或{[La(L)(DMF)]·4(DMF)·0.25(HO)}(DMF为二甲基甲酰胺)(1),并通过单晶X射线衍射、元素分析、热重分析、红外光谱和光致发光研究对其进行了表征。不对称单元包含一个La阳离子、一个阴离子L配体、两个配位的DMF分子、四个游离的DMF分子和四分之一的游离水分子。化合物1具有由La簇和L配体的二级结构单元组成的(3,6)-连接二维kgd拓扑片,这些片通过π-π相互作用进一步堆积成三维超分子网络。由于配体中心激发态,化合物1在室温下表现出光致发光发射,峰值在410 nm处。

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