State Key Laboratory of Applied Organic Chemistry, and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, PR China.
Dalton Trans. 2013 Apr 14;42(14):4822-30. doi: 10.1039/c2dt32674d.
Twelve lanthanide coordination polymers associated with the organic ligand 5-(2′-carboxylphenyl) nicotinic acid (H2cpna): {[Ln(Hcpna)(cpna)(phen)]·H2O}n (Ln = Sm (1), Tb (2), Ho (3), phen = 1,10-phenanthroline), {[Sm(Hcpna)(cpna)(phen)]·2H2O}n (4), {[Ln2(cpna)3(H2O)3]·4H2O}n (Ln = Y (5), Tb(6), Dy (7), Ho (8)), [Lu2(cpna)3(H2O)2]n (9), {[Y2(cpna)3(phen)2(H2O)]·H2O}n (10), and [Ln(cpna)(phen)(NO3)]n (Ln = Tm (11), Lu (12)) have been prepared by hydrothermal methods and structurally characterized. The structure analyses reveal that complexes 1–3 are isostructural and possess unique three-dimensional (3D) frameworks based on the dodecanuclear Sm/Tb/Ho macrocycles. Complex 4 exhibits a one-dimensional (1D) wheel-chain structure, which further builds three-dimensional (3D) supramolecular architecture via O–HN hydrogen-bonding interactions. Complexes 5–8 are also isostructural and display three-dimensional (3D) open frameworks, which possess two types of channels along the a- and b-axis, respectively. Complexes 9 and 10 feature three-dimensional (3D) frameworks and are created from tetranuclear and dinuclear units, respectively. Complexes 11 and 12 are isostructural and demonstrate one-dimensional (1D) double chain structures, which further build three-dimensional (3D) supramolecular architecture via C–H···O hydrogen-bonding. The results show that the pH value of the reaction system, anion, auxiliary ligand and lanthanide contraction play a significant role in determining the structures of the complexes. In addition, the results of luminescent measurements for compounds 2 and 6 in the solid state at room temperature indicate that the different types of structures have a dissimilar influence on their characteristic luminescence. The magnetic properties of compounds 1, 3, 4, 7 and 11 have been investigated. Furthermore, thermal stabilities for 1–12 and the dehydration/hydration properties of compound 6 have also been studied.
十二种与有机配体 5-(2′-羧基苯基)烟酸（H2cpna）配位的镧系元素配合物：{[Ln(Hcpna)(cpna)(phen)]·H2O}n（Ln=Sm（1），Tb（2），Ho（3），phen=1,10-菲啰啉），{[Sm(Hcpna)(cpna)(phen)]·2H2O}n（4），{[Ln2(cpna)3(H2O)3]·4H2O}n（Ln=Y（5），Tb（6），Dy（7），Ho（8）），[Lu2(cpna)3(H2O)2]n（9），{[Y2(cpna)3(phen)2(H2O)]·H2O}n（10）和[Ln(cpna)(phen)(NO3)]n（Ln=Tm（11），Lu（12）），是通过水热法制备的，并进行了结构表征。结构分析表明，配合物 1-3 是同构的，具有基于十二核 Sm/Tb/Ho 大环的独特的三维（3D）框架。配合物 4 呈现一维（1D）轮链结构，通过 O–HN 氢键进一步构建三维（3D）超分子结构。配合物 5-8 也是同构的，具有三维（3D）开放式框架，分别沿 a-和 b-轴具有两种类型的通道。配合物 9 和 10 具有三维（3D）框架，分别由四聚体和二聚体单元构成。配合物 11 和 12 是同构的，呈现一维（1D）双链结构，通过 C–H···O 氢键进一步构建三维（3D）超分子结构。结果表明，反应体系的 pH 值、阴离子、辅助配体和镧系收缩在决定配合物结构方面起着重要作用。此外，室温下化合物 2 和 6 在固态下的发光测量结果表明，不同类型的结构对其特征发光有不同的影响。还研究了化合物 1、3、4、7 和 11 的磁性。此外，还研究了 1-12 的热稳定性以及化合物 6 的脱水/水合性质。
