超分子配位化学研究所
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Fine-Tuning Apertures of Metal−Organic Cages: Encapsulation of Carbon Dioxide in Solution and Solid State

Xiang Zhang, Xia Dong, Weigang Lu, Dong Luo, Xiao-Wei Zhu, Xue Li, Xiao-Ping Zhou,* and Dan Li*



Abstract: Metal-organic cages are potential artificial models for mimicking biological functions due to their capability of selective encapsulation for certain guest molecules. In this work, we designed and synthesized a series of rhombic dodecahedral Ni-imidazolate cages (Ni14L24) with precisely controlled aperture for CO2 encapsulation. The aperture of the cages can be tuned by the strategies of ligand decoration and metal-ion hybridization. Similar to the breathing function of alveoli, CO2 passes through the dynamic aperture into the cages under a pressure of 2.0−3.0 bar in methanol solution, and slowly move out of the cages when the pressure goes down. In the solid state, CO2 is encapsulated and prisoned in the cages under a high pressure of 15.0−30.0 bar or supercritical conditions. By replacing the square-coordinated Ni2+ with Cu2+, the resulting Ni-Cu heteronuclear cage lost the capability of physically encapsulating CO2 even though the aperture’s size is only slightly changed.


文章链接:J Am Chem Soc 2019 11621.pdf