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Microscopic and Mesoscopic Dual Postsynthetic Modifications of Metal–Organic Frameworks
Author(s) -
Lee Byeongchan,
Moon Dohyun,
Park Jinhee
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202000278
Subject(s) - chemistry , metal organic framework , adsorption , alkyl , halide , functional group , sorption , steric effects , crystallography , crystal engineering , crystal (programming language) , inorganic chemistry , crystal structure , stereochemistry , organic chemistry , supramolecular chemistry , polymer , computer science , programming language
We report the dual postsynthetic modification (PSM) of a metal–organic framework (MOF) involving the microscopic conversion of C−H bonds into C−C bonds and the mesoscopic introduction of hierarchical porosity. MOF crystals underwent single‐crystal‐to‐single‐crystal transformations during the electrophilic aromatic substitution of Co 2 ( m ‐DOBDC) ( m ‐DOBDC 4− =4,6‐dioxo‐1,3‐benzenedicarboxylate) with alkyl halides and formaldehyde. The steric hindrance caused by the proximity of the introduced functional groups to the coordination bonds reduced bond stability and facilitated the transformation into hierarchically porous mesostructures by etching with in situ generated protons (hydroniums) and halides. The numerous defect sites in the mesostructural MOFs are potential water‐sorption sites. However, since the introduced functional groups are close to the main adsorption sites, even methyl groups are able to considerably decrease water adsorption, whereas hydroxy groups increase adsorption at low vapor pressures.