Delicate Substituent Effect of Benzene-1,2,3-Tricarboxyl Tectons on Structural Assembly of Unusual Self-Penetrating Coordination Frameworks
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- 作者：Lu-Fang Ma ; Qing-Lei Meng ; Cheng-Peng Li ; Bo Li ; Li-Ya Wang ; Miao Du ; Fu-Pei Liang
- 刊名：Crystal Growth & Design
- 出版年：2010
- 出版时间：July 7, 2010
- 年：2010
- 卷：10
- 期：7
- 页码：3036-3043
- 全文大小：1036K
- 年卷期：v.10,no.7(July 7, 2010)
- ISSN：1528-7505
文摘
Eight ZnII and CdII coordination complexes, {[Zn3(nbta)2(bpy)2(H2O)2](H2O)2}n (1), [Zn4(nbta)2(bpe)2(OH)2]n (2), {[Cd3(nbta)2(bpy)5(H2O)2](H2O)6}n (3), {[Cd3(nbta)2(bpe)2(H2O)2](H2O)2}n (4), [Zn2(Hbta)2(bpy)2(H2O)2](H2O) (5), [Zn(bta)(Hbpe)]n (6), [Cd5(bta)2(Hbta)2(bpy)3(H2O)2]n (7), and {[Cd4(bta)2(bpe)2(H2O)4(OH)2](H2O)2}n (8), were prepared via hydrothermal reactions based on H3nbta or H3bta (H3nbta = 5-nitro-1,2,3-benzenetricarboxylic acid and H3bta = 1,2,3-benzenetricarboxylic acid) and the dipyridyl-type coligand 4,4′-bipyridyl (bpy) or 1,2-di(4-pyridyl)ethene (bpe). All complexes were characterized by elemental analysis, IR spectra, and X-ray powder diffraction techniques. Complexes 1−4 all display unusual three-dimensional (3-D) self-penetrating coordination networks. From the topology point of view, complexes 1 and 2 display the 4-connected frameworks with the Schlfli symbols of (4.104.12)2(43.62.8)2(44.62) and (4.62.72.8)2(42.62.7.8), respectively. Complex 3 features an unprecedented 3-nodal network with (3,5,6)-connectivity and the Schlfli symbol of (52.64.72.86.10)(52.65.72.8)2(52.6)2, also exhibiting an intriguing polyrotaxane entangled motif. Complex 4 shows a new 4-connected (42.63.8)4(64.8.10) topology. Different from 1−4, complexes 5−8 based on H3bta all present the non-self-penetrating structural type. Complex 5 possesses binuclear units which are further extended to a two-dimensional (2-D) supramolecular network via extensive H-bonding interactions, showing alternate left- and right-handed helical chains. Complex 6 has a 2-D layered motif generated via H-bonding interactions between the one-dimensional (1-D) coordination chains. Complex 7 shows a 3-D coordination framework, which is constructed from the 2-D metal-carboxylate layers pillared by the rod-like bipy spacers. Complex 8 presents a 2-D net with the [Cd4(μ3-OH)2]6+ clusters as the linking nodes. These results reveal that the existence of the electron-withdrawing -NO2 group in such a tricarboxyl building block plays a critical role in structural direction of the self-penetrating coordination frameworks.