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Topological Diversity of Coordination Polymers Containing the Rigid Terephthalate and a Flexible N,N′-Type Ligand: Interpenetration, Polyrotaxane, and Polythreading

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journal contribution
posted on 04.06.2008, 00:00 by Guan-Hua Wang, Zhi-Gang Li, Heng-Qing Jia, Ning-Hai Hu, Jing-Wei Xu
Reactions of zinc(II) or cadmium(II) salts with terephthalic acid (H2tp) and 1,3-bis(4-pyridyl)propane (bpp) have afforded four coordination polymers at room temperature, [Zn(μ-tp)(μ-bpp)]n·2nH2O (1), [Cd2(μ-tp)2(μ-bpp)3]n·2nH2O (2), [Cd(μ-tp)(μ-bpp)(H2O)]n·nH2O (3), and [Cd2(μ-tp)(μ-bpp)2(bpp)2Br2]n (4). Single-crystal X-ray diffraction has revealed interesting topological features for these compounds. In 1, the Zn atoms act as 4-connected nodes bridged by the tp and bpp ligands to give a 3-fold interpenetrated 3D network with a unique 66 topology, which is evidently distinct from 4-connected diamondoid networks. 2 represents the first example of a 2-fold interpenetrated coordination polymer, which possesses a 5-connected 3D framework with a unique 610 topology constructed from Cd nodes and tp and bpp spacers. 3 manifests a polyrotaxane motif comprised of two interlocked sets of identical sheets, which result in a 2D → 2D polythreaded layer. Parallel mutual polythreading of 2D layers with dangling bpp ligands is observed in 4, involving five polymeric layers at a time and thus affording a 3D architecture. All compounds were characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis, and their fluorescence properties were also investigated.