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A Comparison of Two Isoreticular Metal‐Organic Frameworks with Cationic and Neutral Skeletons: Stability, Mechanism, and Functionality
Angewandte Chemie International Edition ( IF 12.257 ) Pub Date : 2020-01-14 , DOI: 10.1002/anie.201916649
Ge Huang; Li Yang; Qi Yin; Zhi-Bin Fang; Xiao-Jing Hu; An-An Zhang; Jun Jiang; Tian-Fu Liu; Rong Cao

Although many ionic metal‐organic frameworks (MOFs) have been reported, people still know few about how the charge of skeleton affect the properties of MOF materials. We here for the first time report that the chemical stability of MOFs can be substantially improved through embedding electrostatic interactions in structure. As demonstrated, MOF with a cationic skeleton is impervious to extremely acidic, oxidative, reductive, and high ionic strength conditions such as 12 M HCl (301 days), aqua regia (86 days), H 2 O 2 (30 days), and seawater (30 days), which is surprisingly unprecedented in MOFs. Density functional theory calculations suggested that the cationic framework shows repulsive interaction and large steric hindrance toward the positively charged species in microenvironments, thus protecting the vulnerable dative bonds in structure to achieve high chemical stability. Diverse functionalities can be simultaneously bestowed by substituting the counterions of the charged framework with identically charged functional species, which broadens the horizon in the design of MOFs adaptable to a demanding environment with specific functionalities.
更新日期:2020-01-14

 

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