Microporous Metal–Organic Framework Constructed from Heptanuclear Zinc Carboxylate Secondary Building Units

作者：Qianrong Fang, Guangshan Zhu, Ming Xue, Qing‐Lin Zhang, Jinyu Sun, Xiaodan Guo, Shilun Qiu, Shi‐Tao Xu, Ping Wang, De‐Jun Wang, Yen Wei · 发表于：Chemistry - A European Journal · 年份：2006 · DOI：10.1002/chem.200500963 · 被引用次数：170 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Covalent Organic Framework Applications、Polyoxometalates: Synthesis and Applications

A novel, three-dimensional, noninterpenetrating microporous metal-organic framework (MOF), [Zn7O2(pda)5(H2O)2]5 DMF4 EtOH 6 H2O (1) (H2PDA=p-phenylenediacrylic acid, DMF=N,N-dimethylformamide, EtOH=ethanol), was synthesized by constructing heptanuclear zinc carboxylate secondary building units (SBUs) and by using rigid and linear aromatic carboxylate ligands, PDA. The X-ray crystallographic data reveals that the seven zinc centers of 1 are held together with ten carboxylate groups of the PDA ligands and four water molecules to form a heptametallic SBU, Zn7O4(CO2)10, with dimensions of 9.8 x 9.8 x 13.8 A3. Furthermore, the heptametallic SBUs are interconnected by PDA acting as linkers, thereby generating an extended network with a three-dimensional, noninterpenetrating, intersecting large-channel system with spacing of about 17.3 A. As a microporous framework, polymer 1 shows adsorption behavior that is favorable towards H2O and CH3OH, and substantial H2 uptake. In terms of the heptanuclear zinc carboxylate SBUs, polymer 1 exhibits interesting photoelectronic properties, which would facilitate the exploration of new types of semiconducting materials, especially among MOFs containing multinuclear metal carboxylate SBUs.