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两种含O、N供体配体的铅(II)配合物的合成与物理化学表征。孤对电子功能与晶体结构。

Synthesis and physicochemical characterization of two lead(II) complexes with O-, N-donor ligands. Lone pair functionality and crystal structure.

作者信息

Masternak Joanna, Barszcz Barbara, Hodorowicz Maciej, Khavryuchenko Oleksiy V, Majka Alina

机构信息

Institute of Chemistry, Jan Kochanowski University, 15G Świętokrzyska Str., 25-406 Kielce, Poland.

Institute of Chemistry, Jan Kochanowski University, 15G Świętokrzyska Str., 25-406 Kielce, Poland.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2015 Feb 5;136:1998-2007. doi: 10.1016/j.saa.2014.07.084. Epub 2014 Aug 9.

Abstract

A dinuclear Pb2(4-CHO-5-MeIm)6(NO3)22 (1) and a polynuclear [Pb(2-pzc)2(H2O)]n (2) complexes (where 5(4)-carbaldehyde-4(5)-methylimidazole (5(4)-CHO-4(5)-MeIm) and pyrazine-2-carboxylic acid (2-pzcH)) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. Structural determination for complex 1 reveals a cationic species [Pb(4-CHO-5-MeIm)3]2+ connected through bridging nitrate(V) ions. There are also an uncoordinated nitrate ions as counterions. Complex 2 is a three-dimensional architecture consisting of Pb6O12 building units. The pyrazine-2-carboxylato ligand behaves as a chelating agent and a bi-connective bridge. The coordination polyhedra around lead(II) ion could be described as a distorted docecahedron (1) or monocapped trigonal prism (2). The luminescent properties of 1 and 2 investigated in the solid state at room temperature indicate structure-dependent photoluminescent properties. The DFT calculations and the X-ray structural data point on rather hemidirected type of coordination around Pb(II) ions of 1 and 2.

摘要

已合成双核配合物Pb2(4-CHO-5-MeIm)6(NO3)22 (1)和多核配合物[Pb(2-pzc)2(H2O)]n (2)(其中5(4)-甲醛基-4(5)-甲基咪唑(5(4)-CHO-4(5)-MeIm)和吡嗪-2-羧酸(2-pzcH)),并通过元素分析、红外光谱和X射线晶体学对其进行了表征。配合物1的结构测定表明,其通过桥连硝酸根(V)离子连接形成阳离子物种[Pb(4-CHO-5-MeIm)3]2+。同时还存在未配位的硝酸根离子作为抗衡离子。配合物2是由Pb6O12结构单元组成的三维结构。吡嗪-2-羧酸根配体既作为螯合剂又作为双连接桥。铅(II)离子周围的配位多面体可描述为扭曲的十二面体(1)或单帽三棱柱(2)。在室温下对1和2的固态发光性质研究表明其具有结构依赖性的光致发光性质。DFT计算和X射线结构数据表明1和2中铅(II)离子周围的配位类型为半定向型。

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