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用于金属有机框架一维和二维二级结构单元形成的柔性配体与铜(II)的溶剂效应配位变化

Solvent-Effected Coordination Variation of Flexible Ligands to Cu(II) for the Formation of 1D and 2D Secondary Building Units for Metal-Organic Frameworks.

作者信息

Park Jiwon, Koo Jin Young, Choi Hee Cheul

机构信息

Department of Chemistry, Pohang University of Science and Technology (POSTECH), 77, Cheongam-ro, Nam-Gu, Pohang-si, Korea 37673.

出版信息

Inorg Chem. 2021 Apr 5;60(7):5376-5382. doi: 10.1021/acs.inorgchem.1c00361. Epub 2021 Mar 25.

Abstract

Producing more than one structure from the same set of metal and ligand precursors will grant structural diversity in metal-organic framework (MOF) systems. One of the biggest obstacles of getting structural diversity for the late transition metals is that the coordination mode is pretty much fixed by nature. Herein, we show that two different coordination modes to Cu(II) are possible for flexible ligands containing hydrophilic terminal groups through solvent guidance. It is demonstrated that ,-muconic acid (Hmuco) ligands coordinate to Cu(II) to form Cu(II) muconate MOFs having a 1D chain structure and a 2D plane structure in water-rich and DMF-rich water-DMF mixed solvent systems, respectively. It is suggested that the interaction between ligands and solvent is responsible for the selective coordination. A similar result was observed from the attempts using the fumaric acid ligand. Our results provide a new direction to obtain diverse secondary building units for the construction of diverse MOFs.

摘要

从同一组金属和配体前体生成不止一种结构将赋予金属有机框架(MOF)体系结构多样性。对于后过渡金属而言,获得结构多样性的最大障碍之一是其配位模式本质上几乎是固定的。在此,我们表明,通过溶剂引导,对于含有亲水性端基的柔性配体,与Cu(II)存在两种不同的配位模式。结果表明,在富含水和富含N,N - 二甲基甲酰胺(DMF)的水 - DMF混合溶剂体系中,己二酸(Hmuco)配体分别与Cu(II)配位形成具有一维链状结构和二维平面结构的己二酸铜MOF。研究表明,配体与溶剂之间的相互作用导致了选择性配位。使用富马酸配体进行尝试时也观察到了类似结果。我们的结果为获得用于构建多样MOF的多样二级结构单元提供了新方向。

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