Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 141, Issue 29, Pages 11621-11627Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b04520
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Funding
- National Natural Science Foundation of China [21731002, 91222202, 21871172, 21371113]
- Guangdong Natural Science Funds for Distinguished Young Scholar [2014A030306042]
- Beijing National Laboratory for Molecular Sciences [BNLMS20160139]
- Jinan University
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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.
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