State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 35002, China.
Inorg Chem. 2012 Jan 2;51(1):523-30. doi: 10.1021/ic201986m. Epub 2011 Dec 2.
Eight three-dimensional lanthanide-thiophene-2,5-dicarboxylate frameworks, [Ln(TDC)(2)]·(choline) (1-6; Ln = Gd, Nd, Eu, Er, Tb, Dy; TDC = thiophene-2,5-dicarboxylate), [Yb(TDC)(2)(e-urea)]·(choline)·H(2)O (7; e-urea = ethyleneurea), [Nd(2)(TDC)(3)(e-urea)(4)]·3(e-urea) (8) have been successfully prepared in deep eutectic solvents (choline chloride/e-urea), respectively. Compounds 1-7 are anionic frameworks with 8-connected bcu topology, while compound 8 features a neutral 6-connected rob-type framework with guest e-urea molecules. In these structures, lanthanide ions show dicapped trigonal prism, pentagonal bipyramid, and tricapped trigonal prism coordination configurations, respectively, and the TDC ligands exhibit different coordination modes. Versatile helical substructures are presented in these compounds. The photoluminescent properties of compounds 3 (Eu) and 8 (Nd) were studied. Moreover, compound 8 can perform single-crystal-to-single-crystal guest exchange. The ethanol-exchange mechanism of 8 can be ascribed to the kinetically controlled flexibility (KCF).
八个三维镧系元素-噻吩-2,5-二羧酸酯框架，[Ln(TDC)(2)]·(胆碱)（1-6；Ln = Gd、Nd、Eu、Er、Tb、Dy；TDC = 噻吩-2,5-二羧酸酯），[Yb(TDC)(2)(e-urea)]·(胆碱)·H(2)O（7；e-urea = 乙烯脲），[Nd(2)(TDC)(3)(e-urea)(4)]·3(e-urea)（8），分别在深共晶溶剂（胆碱氯化物/乙烯脲）中成功制备。化合物 1-7 是具有 8 连接 bcu 拓扑结构的阴离子骨架，而化合物 8 具有中性 6 连接 rob 型骨架，具有客体 e-urea 分子。在这些结构中，镧系元素离子分别呈现双帽三角棱柱、五重双锥和三帽三角棱柱配位构型，而 TDC 配体呈现不同的配位模式。这些化合物中呈现出多种螺旋亚结构。研究了化合物 3（Eu）和 8（Nd）的光致发光性质。此外，化合物 8 可以进行单晶到单晶客体交换。8 的乙醇交换机制可以归因于动力学控制的灵活性（KCF）。
