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A Comparison of Two Isoreticular Metal–Organic Frameworks with Cationic and Neutral Skeletons: Stability, Mechanism, and Catalytic Activity
Author(s) -
Huang Ge,
Yang Li,
Yin Qi,
Fang ZhiBin,
Hu XiaoJing,
Zhang AnAn,
Jiang Jun,
Liu TianFu,
Cao Rong
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201916649
Subject(s) - cationic polymerization , steric effects , chemistry , counterion , ionic bonding , catalysis , ionic strength , metal organic framework , lone pair , chemical physics , inorganic chemistry , ion , polymer chemistry , molecule , stereochemistry , organic chemistry , aqueous solution , adsorption
Although many ionic metal–organic frameworks (MOFs) have been reported, little is known about how the charge of the skeleton affects the properties of the MOF materials. Herein we report how the chemical stability of MOFs can be substantially improved through embedding electrostatic interactions in structure. A 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 unprecedented for MOFs. DFT calculations suggested that steric hinderance and the repulsive interaction of the cationic framework toward positively charged species in microenvironments protects the vulnerable bonds in the structure. Diverse functionalities can be 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.