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首页> 外文期刊>Crystal growth & design >One-, Two-, and Three-Dimensional Lanthanide Complexes Constructed from Pyridine-2,6-dicarboxylic Acid and Oxalic Acid Ligands
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One-, Two-, and Three-Dimensional Lanthanide Complexes Constructed from Pyridine-2,6-dicarboxylic Acid and Oxalic Acid Ligands

机译：由吡啶-2,6-二羧酸和草酸配体构成的一维，二维和三维镧系元素络合物

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摘要

The reaction of pyridine-2,6-dicarboxylic acid (HPDA) and oxalic acid (H(2)ox) with Ln(2)O(3)/Ce(NO3)(3) under hydrothermal conditions generated a series of new one-, two-, and three-dimensional (1D, 2D, and 3D) coordination polymers, namely, {[Ln(PDA)(ox)(0.5)(H2O)(3)]center dot H2O}(n) (Ln = La(1) and Ce(2)), {[Ln(2)(PDA)(ox)(2)center dot 4(H2O)]}(n) (Ln = Nd(3) and Sm(4)), {[Ln(2)(PDA)(ox)(2)center dot 7(H2O)]}(n) (Ln = Eu(5), Tb(6), and Er(7)) (PDA(2-) = pyridine-2,6-dicarboxylate anion, ox(2-) = oxalate anion). The complexes were characterized by X-ray single-crystal determination, spectroscopy and fluorescent analyses. Compounds I and 2 (type I structure) are 1D zigzag chain structures bridged by bis-bidentate oxalate. The 1D chains are further linked by the significant intermolecular pi center dot center dot center dot pi interactions between pyridine rings of coordinating PDA(2-) groups to form a 2D supramolecular framework network. In compounds 3 and 4 (type II structure), the square motifs formed by four Ln(III) ions, serving as the building blocks, are assembled into a highly ordered 2D (4,4) grid. Similarly, via weak pi center dot center dot center dot pi interactions between two central pyridine rings from two adjacent sheets, the 2D layers are further stacked up into the final 3D structures. Complexes 5, 6, and 7 (type III structure) are isomorphous and have the same 3D network structures fabricated through two alternately arranging hexanuclear Ln(3+) (Ln = Eu(5), Tb(6) and Er(7)) units, and the guest water molecules are trapped in the cavity. The progressive structural variation from the I D zigzag chains (1-2) to 2D networks (3-4) and to 3D frameworks (5, 6, and 7) is attributed to the lanthanide contraction effect and the different coordination modes of PDA(2-). Two new coordination modes of pyridine-2,6-dicarboxylic acid are observed, which proved that pyridine-2,6-dicarboxylic acid could be used as an effective bridging ligand to construct lanthanide-based coordination polymers. The fluorescent properties of compounds 3, 5, and 6 have also been investigated.
机译：在水热条件下，吡啶2,6-二羧酸（HPDA）和草酸（H（2）ox）与Ln（2）O（3）/ Ce（NO3）（3）的反应产生了一系列新的-，二维和三维（1D，2D和3D）配位聚合物，即{[Ln（PDA）（ox）（0.5）（H2O）（3）]中心点H2O}（n）（Ln = La（1）和Ce（2）），{[Ln（2）（PDA）（ox）（2）中心点4（H2O）]}（n）（Ln = Nd（3）和Sm（4） ），{[Ln（2）（PDA）（ox）（2）中心点7（H2O）]}（n）（Ln = Eu（5），Tb（6）和Er（7））（PDA（ 2-）=吡啶2,6-二羧酸根阴离子，ox（2-）=草酸根阴离子）。通过X射线单晶测定，光谱学和荧光分析来表征复合物。化合物I和2（I型结构）是一双锯齿状草酸酯桥接的一维之字形链结构。 1D链进一步通过配位的PDA（2-）基团的吡啶环之间的重要分子间pi中心点pi中心点pi中心点pi相互作用形成2D超分子框架网络。在化合物3和4（II型结构）中，由四个Ln（III）离子（作为构建基块）形成的方形图案被组装成高度有序的2D（4,4）网格。类似地，通过来自两个相邻片的两个中心吡啶环之间的弱pi中心点中心点中心点pi相互作用，将2D层进一步堆叠为最终的3D结构。配合物5、6和7（III型结构）是同构的，并且具有通过两个交替排列的六核Ln（3 +）（Ln = Eu（5），Tb（6）和Er（7））制造的相同3D网络结构。单位，客体水分子被困在腔中。从ID之字形链（1-2）到2D网络（3-4）和3D框架（5、6和7）的渐进结构变化归因于镧系元素收缩效应和PDA（2）的不同配位模式-）。观察到吡啶2，6-二羧酸的两种新的配位方式，证明吡啶2，6-二羧酸可作为一种有效的桥联配体来构建基于镧系元素的配位聚合物。还研究了化合物3、5和6的荧光性质。

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