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Two- and Three-Dimensional Lanthanide Complexes:  Synthesis, Crystal Structures, and Properties

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posted on 30.04.2007, 00:00 by Jun Xia, Bin Zhao, Hong-Sheng Wang, Wei Shi, Yue Ma, Hai-Bin Song, Peng Cheng, Dai-Zheng Liao, Shi-Ping Yan
3,5-Pyrazoledicarboxylic acid (H3L) reacts with nitrate salts of lanthanide(III) (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er) under hydrothermal conditions to form a series of lanthanide polymers 19. These nine polymers have the same crystal system of monoclinic, but they exhibit three different kinds of metal−organic framework structures. The complexes {[Ln2(HL)3(H2O)4]·2H2O}n (Ln = Pr (1), Nd (2), and Sm (3)) were isostructural and exhibited porous 3D frameworks with a Cc space group. The complexes {[Ln2(HL)3(H2O)3]·3H2O}n (Ln = Eu (4), Gd (5), and Tb (6)) were isostructural and built 2D double-decker (2DD) frameworks with a P21/c space group. The complexes {[Ln(HL)(H2L)(H2O)2]}n ((Ln = Dy (7), Ho (8), and Er (9)) were also isostructural and formed 2D monolayer (2DM) frameworks with a P21/n space group. The structure variation from the 3D porous framework to the 2D double-decker to the 2D monolayer is attributed to the lanthanide contraction effect. Notably, six new coordination modes of 3,5-pyrazoledicarboxylic acid were observed, which proved that 3,5-pyrazoledicarboxylic acid may be used as an effective bridging ligand to assemble lanthanide-based coordination polymers. The photophysical and magnetic properties have also been investigated.