Wang Hai-Hua, Jia Li-Na, Hou Lei, Shi Wen-juan, Zhu Zhonghua, Wang Yao-Yu
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Materials Science, Northwest University , Xi'an 710127, P. R. China.
Inorg Chem. 2015 Feb 16;54(4):1841-6. doi: 10.1021/ic502733v. Epub 2015 Jan 30.
By a less-exploited strategy, a stable framework was constructed by using 4,4'-biphenyldicarboxylic acid (H2bpdc) and methyl-functionalized 3,3',5,5'-tetramethyl-4,4'-bipyrazole (H2bpz) coligands, revealing a new (6,8)-connected net based on two extremely rare trinuclear and tetranuclear metal-carboxylate-pyrazolate clusters. The framework is very porous and possesses not only high CO2 loadings but also very high CO2/N2 selectivities at 308 and 313 K because of the polar pore surface decorated by clusters, pyrazolyl units, and confined cages with methyl groups dangling. Importantly, GCMC simulation identified two favorable CO2 sorption sites located sequentially near Co3(pz)3 and Co3(CO2)2(pz) motifs of the tetranuclear cluster, and the multipoint framework-CO2 interactions were distinguished. The framework also displays remarkable stability toward water and organic solvents.
通过一种较少被采用的策略，利用4,4'-联苯二甲酸（H2bpdc）和甲基官能化的3,3',5,5'-四甲基-4,4'-联吡唑（H2bpz）共配体构建了一个稳定的框架，揭示了一种基于两个极其罕见的三核和四核金属羧酸盐-吡唑酸盐簇的新型（6,8）连接网络。该框架具有很高的孔隙率，由于簇、吡唑基单元以及带有悬挂甲基的受限笼装饰的极性孔表面，在308 K和313 K时不仅具有高的CO2负载量，而且具有非常高的CO2/N2选择性。重要的是，巨正则蒙特卡罗模拟确定了两个有利的CO2吸附位点，依次位于四核簇的Co3(pz)3和Co3(CO2)2(pz)基序附近，并且区分了多点框架-CO2相互作用。该框架对水和有机溶剂也表现出显著的稳定性。
