pH-dependent assembly of 0D to 3D Keggin-based coordination polymers: structures and catalytic properties.
pH-dependent assembly of 0D to 3D Keggin-based coordination polymers: structures and catalytic properties.
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DOI：
10.1039/b911606k
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发表时间：
2009-10
影响因子：
4
通讯作者：
F. Yu;Xiang‐Jian Kong;Yun-Yun Zheng-Yun;Yanping Ren;L. Long;Rong-Bin Huang;Lan-Sun Zheng
中科院分区：
文献类型：
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作者：
F. Yu;Xiang‐Jian Kong;Yun-Yun Zheng-Yun;Yanping Ren;L. Long;Rong-Bin Huang;Lan-Sun Zheng
四种基于 Keggin 的配位聚合物，即 {[Cu2(4,4'-bpy)(4,4'-Hbpy)4(H2O)4](SiW12O40)2(H2O)4}n (1)， {[Cu2(4,4'-bpy)(4,4'-Hbpy)6(SiW12O40)3](4,4'-Hbpy)2(H2O)7}n (2), {[Cu2(mu2-H2O)2(4,4'-bpy)3(SiW12O40)](H2O)6}n (3) 和 通过硅钨酸的水热反应制备{[Cu2(mu2-OH)(4,4'-bpy)3(SiW12O40)(H2O)][Cu2(mu2-O)(4,4'-bpy)4(H2O)2]0.5 x (H2O)3}n (4) (4,4'-bpy = 4,4'-联吡啶)， 不同pH条件下的硝酸铜(II)和4,4'-联吡啶。配位聚合物 1 和 2 分别具有 0D 和 1D 结构，在 pH = 3.5 下制备。在pH=5.5时，得到2D配位聚合物3。将反应的 pH 值提高到 8.5，得到 3D 配位聚合物 4。1-4 的结构多样性表明，反应的 pH 值在基于 POM 的配位聚合物的组装中起着关键作用。 1-4对乙苯氧化催化性能的研究表明，配位聚合物的催化活性与配位聚合物中4,4'-bpy的质子化程度密切相关。
Four Keggin-based coordination polymers, namely, {[Cu2(4,4'-bpy)(4,4'-Hbpy)4(H2O)4](SiW12O40)2(H2O)4}n (1), {[Cu2(4,4'-bpy)(4,4'-Hbpy)6(SiW12O40)3](4,4'-Hbpy)2(H2O)7}n (2), {[Cu2(mu2-H2O)2(4,4'-bpy)3(SiW12O40)](H2O)6}n (3) and {[Cu2(mu2-OH)(4,4'-bpy)3(SiW12O40)(H2O)] [Cu2(mu2-O)(4,4'-bpy)4(H2O)2]0.5 x (H2O)3}n (4) (4,4'-bpy = 4,4'-bipyridine) were prepared through the hydrothermal reaction of silicotungstic acid, copper(II) nitrate and 4,4'-bipyridine under different pH conditions. Coordination polymers 1 and 2, which exhibit 0D and 1D structures respectively, were prepared at pH = 3.5. At pH = 5.5, a 2D coordination polymer 3 was obtained. Increasing the pH of the reaction to 8.5 led to a 3D coordination polymer 4. The structural diversities of 1-4 reveal that the pH value of the reaction plays a key role in the assembly of POM-based coordination polymers. Investigation of the catalytic properties of 1-4 for the oxidation of ethylbenzene indicates that the catalytic activity of the coordination polymers is closely related to the protonated extent of 4,4'-bpy in the coordination polymers.