Adjusting the Porosity and Interpenetration of Cadmium(II) Coordination Polymers by Ligand Modification: Syntheses, Structures, and Adsorption Properties
Adjusting the Porosity and Interpenetration of Cadmium(II) Coordination Polymers by Ligand Modification: Syntheses, Structures, and Adsorption Properties
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通过配体修饰调节镉(II)配位聚合物的孔隙率和互穿：合成、结构和吸附性能
DOI：
10.1021/cg900980y
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发表时间：
2010-03-01
影响因子：
3.8
通讯作者：
Bu, Xian-He
中科院分区：
文献类型：
--
作者：
Li, Zuo-Xi;Hu, Tong-Liang;Bu, Xian-He
1，4-双（咪唑-1-基）苯（L-1）、1，4-双（苯并咪唑-1-基）苯（L-2）和4，4 '-双（苯并咪唑-1-基）联苯（L-3）等一系列结构相关的刚性咪唑配体已被用于构建配位聚合物。CdX_2（X = BF_4 ~-或ClO_4 ~-）与这些配体反应，得到三个新的三维网络：{[Cd（L-1）（3）]（BF_4）（2）（CHCl_3）（2）}（无穷大）（1），{[Cd（L-2）（3）]（ClO_4）（2）（CHCl_3）（4）（CH_3OH）（2）}（无穷大）（2）和{[Cd（L-3）（3）]（ClO_4）（2）}（无穷大）（3）。化合物1-3都是基于六个连接的Cd-II节点的α-Po金属有机框架（MOFs），所述节点由配体分子的六个氮原子八面体配位。配合物2代表一个扭曲的非互穿的α-Po骨架，而1和3都表现出双互穿的α-Po网络。这些结果表明，互穿的程度是可调的配体修饰，即，不同的配体间隔或末端基团。这三种配合物在其网络中表现出不同的空隙体积。气体吸附实验表明，3对CO2具有中等的气体吸附能力，且吸附-脱附过程是可逆的。
A series of structurally related rigid imidazole ligands, 1,4-bis(imidazol-1-yl)benzene (L-1), 1,4-bis(benzoimidazol-1-yl)benzene (L-2), and 4,4'-bis(benzoimidazol-1-yl)biphenyl (L-3), have been utilized to construct coordination polymers. The reactions of CdX2 (X = BF4- or ClO4-) with these ligands afford three new three-dimensional networks, {[Cd(L-1)(3)](BF4)(2)(CHCl3)(2)}(infinity) (1), {[Cd(L-2)(3)]ClO4)(2)(CHCl3)(4)(CH3OH)(2)}(infinity) (2), and {[Cd(L-3)(3)](ClO4)(2)}(infinity) (3). Compounds 1-3 are all alpha-Po metal-organic frameworks (MOFs) based on six-connected Cd-II nodes which are octahedrally coordinated by six nitrogen atoms of ligand molecules. Complex 2 represents a distorted alpha-Po framework with noninterpenetration, whereas 1 and 3 both exhibit a double interpenetrating alpha-Po network. These results suggest that the degree of interpenetration is tunable by ligand modifications, that is, varying the ligand spacer or terminal group. The three complexes exhibit a different void volume in their network. Gas adsorption measurements indicate that 3 possesses moderate gas-adsorption ability for CO2, and the progress of adsorption and desorption is reversible.