MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, PR China.
Inorg Chem. 2011 Mar 21;50(6):2321-8. doi: 10.1021/ic102015g. Epub 2011 Feb 22.
A microporous coordination polymer, namely, Co(3)(ina)(4)(OH)(C(2)H(5)OH)(3)·C(2)H(5)OH·(H(2)O)(3) (1, or MCF-38, ina = isonicotinate), with 8-connected {Co(3)(OH)} clusters as the structural secondary building units, has been solvothermally synthesized. The hydroxo-centered Co(II) cluster involves multiple active metal sites. The interesting apical ligand substitutions have been directly observed, and the corresponding products of Co(3)(ina)(4)(OH)(G)(x)(H(2)O)(n)·G·(H(2)O)(m) (1 ⊃ PrOH, G = PrOH, x = 2, n = 1, m = 3; 1 ⊃ BuOH, G = BuOH, x = 2, n = 1, m = 1, and 1 ⊃ MeOH, G = MeOH, x = 3, n = 0, m = 7) have also been obtained by solvothermal syntheses or crystal-to-crystal transformations. High-pressure H(2) adsorption measurement at 77 K reveals that activated 1 can absorb 2.2 wt % H(2) at 5 bar. The relative H(2) absorption at low pressure (86% of the storage capacity at 1 bar) is higher than the corresponding values reported for some typical porous coordination polymers. The magnetic studies of 1 show a dominant antiferromagnetic coupling between Co(II) ions of intra- and inter-cluster.
一种微孔配位聚合物，即Co(3)(ina)(4)(OH)(C(2)H(5)OH)(3)·C(2)H(5)OH·(H(2)O)(3)（1，或 MCF-38，ina = 异烟酸），以 8 连接的{Co(3)(OH)}簇作为结构次级构建单元，已通过溶剂热合成得到。羟基中心的 Co(II)簇涉及多个活性金属位点。已经直接观察到有趣的顶点配体取代，并且相应的产物Co(3)(ina)(4)(OH)(G)(x)(H(2)O)(n)·G·(H(2)O)(m)（1 ⊃ PrOH，G = PrOH，x = 2，n = 1，m = 3；1 ⊃ BuOH，G = BuOH，x = 2，n = 1，m = 1，和 1 ⊃ MeOH，G = MeOH，x = 3，n = 0，m = 7）也已通过溶剂热合成或晶到晶转变得到。在 77 K 下进行的高压 H(2)吸附测量表明，活化的 1 在 5 bar 下可吸收 2.2wt%的 H(2)。在低压下的相对 H(2)吸收（在 1 bar 下的存储容量的 86%）高于一些典型的多孔配位聚合物的相应值。1 的磁性研究表明，簇内和簇间的 Co(II)离子之间存在主导的反铁磁耦合。
