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由吡啶-2,6-二羧酸 N-氧化物组装而成的一维螺旋、二维砖墙和人字形以及三维互穿 d10 金属有机骨架结构。

1D helix, 2D brick-wall and herringbone, and 3D interpenetration d10 metal-organic framework structures assembled from pyridine-2,6-dicarboxylic acid N-oxide.

作者信息

Wen Li-Li, Dang Dong-Bin, Duan Chun-Ying, Li Yi-Zhi, Tian Zheng-Fang, Meng Qing-Jin

机构信息

Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, PR China.

出版信息

Inorg Chem. 2005 Oct 3;44(20):7161-70. doi: 10.1021/ic0509985.

Abstract

Five novel interesting d(10) metal coordination polymers, [Zn(PDCO)(H2O)2]n (PDCO = pyridine-2,6-dicarboxylic acid N-oxide) (1), [Zn2(PDCO)2(4,4'-bpy)2(H2O)2.3H2O]n (bpy = bipyridine) (2), [Zn(PDCO)(bix)]n (bix = 1,4-bis(imidazol-1-ylmethyl)benzene) (3), [Zn(PDCO)(bbi).0.5H2O]n (bbi = 1,1'-(1,4-butanediyl)bis(imidazole)) (4), and [Cd(PDCO)(bix)(1.5).1.5H2O]n (5), have been synthesized under hydrothermal conditions and structurally characterized. Polymer 1 possesses a one-dimensional (1D) helical chainlike structure with 4(1) helices running along the c-axis with a pitch of 10.090 Angstroms. Polymer 2 has an infinite chiral two-dimensional (2D) brick-wall-like layer structure in the ac plane built from achiral components, while both 3 and 4 exhibit an infinite 2D herringbone architecture, respectively extended in the ac and ab plane. Polymer 5 features a most remarkable and unique three-dimensional (3D) porous framework with 2-fold interpenetration related by symmetry, which contains channels in the b and c directions, both distributed in a rectangular grid fashion. Compounds 1-5, with systematic variation in dimensionality from 1D to 2D to 3D, are the first examples of d(10) metal coordination polymers into which pyridinedicarboxylic acid N-oxide has been introduced. In addition, polymers 1, 4, and 5 display strong blue fluorescent emissions in the solid state. Polymer 3 exhibits a strong SHG response, estimated to be approximately 0.9 times that of urea.

摘要

合成了五种新型有趣的d(10)金属配位聚合物,即[Zn(PDCO)(H₂O)₂]ₙ(PDCO = 吡啶-2,6-二羧酸N-氧化物)(1)、[Zn₂(PDCO)₂(4,4'-bpy)₂(H₂O)₂·3H₂O]ₙ(bpy = 联吡啶)(2)、[Zn(PDCO)(bix)]ₙ(bix = 1,4-双(咪唑-1-基甲基)苯)(3)、[Zn(PDCO)(bbi)·0.5H₂O]ₙ(bbi = 1,1'-(1,4-丁二醇)双(咪唑))(4)和[Cd(PDCO)(bix)(1.5)·1.5H₂O]ₙ(5),并对其进行了结构表征。聚合物1具有一维(1D)螺旋链状结构,4(1)个螺旋沿c轴延伸,螺距为10.090埃。聚合物2在ac平面具有由非手性组分构建的无限手性二维(2D)砖墙状层结构,而3和4均呈现无限二维人字形结构,分别在ac和ab平面延伸。聚合物5具有最显著和独特的三维(3D)多孔框架,通过对称相关的2倍互穿,在b和c方向包含通道,均以矩形网格方式分布。化合物1 - 5,维度从1D到2D再到3D有系统变化,是引入吡啶二羧酸N-氧化物的d(10)金属配位聚合物的首例。此外,聚合物1、4和5在固态下显示出强烈的蓝色荧光发射。聚合物3表现出强烈的SHG响应,估计约为尿素的0.9倍。

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