State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China.
Chemistry. 2009 Nov 16;15(45):12496-502. doi: 10.1002/chem.200900520.
The syntheses, structures, and characterization of six Ln(3+)-Cu(2+)-glycine (Hgly) coordination polymers are described in this paper. They represent three types of structures. Type I (Ln=La (1), Pr (2), and Sm (3)) is a 1D catenarian polymer comprising [Ln(2)] nodes bridged by four cis-Cu(gly)(2) linkers. Type II (Ln=Eu (4) and Dy (5)) is a 2D open framework with a 4(4)-net, composed of novel [Ln(6)Cu(22)] cluster nodes linked by trans-Cu(gly)(2) linkers. Furthermore, the inner structures of the [Ln(6)Cu(22)] nodes, and the connection mode between the nodes and linkers are slightly different for 4 and 5. Type III (Ln=Er (6)) is a 3D open framework with a novel 3(6)4(18)5(3)6 topology, made up of [Er(6)Cu(24)] cluster nodes and trans-Cu(gly)(2) linkers. The rich variety of the resulting structures owes itself mainly to the interselection between the dynamic control of metalloligands and cationic components. A transition from frequency dependence to frequency independence is observed in the field-induced magnetization lag for 1-3. The frequency dependence at low temperatures may come from the antiferromagnetic Cu--Cu interaction through the [Ln(2)] nodes, whereas the frequency independence may be due to the disappearance of the antiferromagnetic Cu--Cu interaction at high temperatures.
本文描述了六种 Ln(3+)-Cu(2+)-甘氨酸（Hgly）配位聚合物的合成、结构和表征。它们代表了三种结构类型。类型 I（Ln=La（1）、Pr（2）和 Sm（3））是由[Ln(2)]节点通过四个顺式-Cu(gly)(2)连接体桥接而成的一维链聚合物。类型 II（Ln=Eu（4）和 Dy（5））是具有 4(4)-网的二维开放骨架，由通过反式-Cu(gly)(2)连接体连接的新型[Ln(6)Cu(22)]簇节点组成。此外，4 和 5 之间的[Ln(6)Cu(22)]节点的内部结构和节点与连接体的连接方式略有不同。类型 III（Ln=Er（6））是具有新型 3(6)4(18)5(3)6拓扑结构的三维开放骨架，由[Er(6)Cu(24)]簇节点和反式-Cu(gly)(2)连接体组成。丰富的结构多样性主要归因于金属配合物和阳离子成分之间的动态控制的相互选择。在 1-3 中，观察到磁场诱导磁化滞后从频率相关到频率无关的转变。低温下的频率依赖性可能来自通过[Ln(2)]节点的反铁磁 Cu--Cu 相互作用，而高温下的频率独立性可能是由于反铁磁 Cu--Cu 相互作用的消失。
