Isoreticular Metal-Organic Polyhedral Networks Based on 5-Connecting Paddlewheel Motifs
Isoreticular Metal-Organic Polyhedral Networks Based on 5-Connecting Paddlewheel Motifs
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DOI：
10.1021/ic801784j
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发表时间：
2009-03-02
影响因子：
4.6
通讯作者：
Seo, Jinwoo
中科院分区：
文献类型：
--
作者：
Chun, Hyungphil;Jung, Heejin;Seo, Jinwoo
具有独特的5连接拓扑结构的金属有机多面体网络被扩展成使用不同金属离子或二羧酸配体的系列。原型材料（ZmID）， [Zn-4(MiP)(4)(dabco)(OH2)(2)] （MiP = 5-甲基间苯二甲酸酯，dabco =重氮杂环[2.2.2]辛烷），基于5连接桨轮图案，具有大的笼状孔隙（8-20埃直径）。金属离子被Co2+和/或二羧酸盐被二苯二甲酸盐（ip）或2,7-萘二羧酸盐（2,7-ndc）取代，得到等垂直骨架[Zn-4(ip)(4)(dabco)(OH2)(2)] (ZID), [Co4O4(dabco)(OH2)(2)] （CID）和[Zn-4(2,7-ndc)(4)(dabco)(OH2)(2)] （ZND）。x射线粉末衍射和气体吸附研究表明，ZID和CID具有可持续的孔隙结构，并且比ZmID具有更高的N-2吸收量。发现ZND在客体溶剂的去除方面不稳定。ZmID， ZID和CID在H-2吸附量（在77 K和1 bar时为1.4-1.5 wt %）和H2吸附等容热（低覆盖时为6-7 kJ/mol）方面都是相似的。
A metal-organic polyhedral network with a unique 5-connected topology is expanded into a series using different metal ions or dicarboxylate ligands. The prototype material (ZmID), [Zn-4(MiP)(4)(dabco)(OH2)(2)] (mip = 5-methylisophthalate, dabco = diazabicyclo[2.2.2]octane), is based on 5-connecting paddlewheel motifs and possesses large cage-like pores (8-20 angstrom diameter). The metal ion is replaced by Co2+ and/or the dicarboxylate by isophthalate (ip) or 2,7-naphthalenedicarboxylate (2,7-ndc) to give isoreticular frameworks [Zn-4(ip)(4)(dabco)(OH2)(2)] (ZID), [Co4O4(dabco)(OH2)(2)] (CID), and [Zn-4(2,7-ndc)(4)(dabco)(OH2)(2)] (ZND). X-ray powder diffraction and gas sorption studies reveal that ZID and CID have sustainable pore structures and show higher N-2 uptakes than ZmID. ZND is found unstable with respect to the removal of guest solvents. ZmID, ZID, and CID are all similar in terms of the H-2 sorption capacities (1.4-1.5 wt % at 77 K and 1 bar) and isosteric heat of H2 adsorption (6-7 kJ/mol at low coverage).