Chain, Pillar, Layer, and Different Pores: A N-[(3-Carboxyphenyl)-sulfonyl]glycine Ligand as a Versatile Building Block for the Construction of Coordination Polymers

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• 作者：Lu-Fang Ma ; Li-Ya Wang ; Xian-Kuan Huo ; Yao-Yu Wang ; Yao-Ting Fan ; Jian-Ge Wang ; Shu-Hui Chen
• 刊名：Crystal Growth & Design
• 出版年：2008
• 出版时间：February 2008
• 年：2008
• 卷：8
• 期：2
• 页码：620 - 628
• 全文大小：2903K
• 年卷期：v.8,no.2(February 2008)
• ISSN：1528-7505

文摘

Five novel coordination polymers containing N-[(3-carboxyphenyl)-sulfonyl]glycine (H₃L), namely [Co₃L₂(μ₂-bipy)₂(H₂O)₆]_n·2nCH₃OH·8nH₂O (1), [Mn(HL)(μ₂-bipy)(H₂O)₂]_n·nH₂O (2), [Mn(HL)(μ₂-bipy)(H₂O)]_n·3nH₂O (3), [Mn(HL)(bipy)(μ₂-bipy)_0.5(H₂O)]_n·4nH₂O (4), [Ca(H₂O)₄Cu₂(μ₂-bipy)₂L₂]_n·4nH₂O (5) (bipy = 4,4′-bipyridine), were prepared under control by tuning the reaction conditions such as pH value, reaction temperature, and starting materials. X-ray structural analyses of 1–5 reveal their structural diversity ranging from one-dimensional (1D) (1), two-dimensional (2D) (2), and noninterpenetrating 3-D porous coordination polymers (3, 4) to a 2-fold 3D interpenetrating network (5). Compound 1 presents a 1D chain structure with alternating [CoL(H₂O)]₂²⁻ binuclear and [Co(4,4′-bipy)₂(H₂O)₄]²⁺ mononuclear units along the a-axis. Polymer 2, which was formed at a comparatively lower temperature, has a 2D structure extended by a HL²⁻ ligand and a monopillar of bipy. A higher temperature was used in the preparation of 3 and 4. In addition, 3 was synthesized also at a higher pH value. In 3, HL²⁻ ligands link the metal ions to form 2D wavelike rectangle-grid layers which are held together through μ₂-bipy molecules in a double-pillar supporting fashion to give a 3D porous framework. A decrease of the pH value led to the formation of another 3D porous framework 4, in which each Mn center binds two trans-located bipy molecules. One bipy behaves as a terminal ligand, while the other one acts as a bridging ligand extending the 2D layers into a unique 3D porous framework. When calcium hydroxide was used, it led to the construction of a 2-fold 3D interpenetrating network of 5 where the Cu atoms are joined by bipy ligands to generate a 1D zigzag chain. The thermogravimetric (TG) and powder X-ray diffraction (PXRD) measurements reveal that both 3 and 4 are stable after dehydration. All of these suggest that the ligand of H₃L is a versatile building block for the construction of metal organic frameworks (MOFs).