Experimental, Structural, and Computational Investigation of Mixed Metal-Organic Frameworks from Regioisomeric Ligands for Porosity Control
2020
Porosity
control and structural analysis of metal–organic
frameworks (MOFs) can be achieved using regioisomeric ligand mixtures.
While ortho-dimethoxy-functionalized MOFs yielded
highly porous structures and para-dimethoxy-functionalized
MOFs displayed almost nonporous properties in their N2 isotherms
after evacuation, regioisomeric ligand-mixed MOFs showed variable
N2 uptake amount and surface area depending on the ligand-mixing
ratio. The quantity of N2 absorbed was tuned between 20
and 300 cm3/g by adjusting the ligand-mixing ratio. Both
experimental analysis and computational modeling were performed to
understand the porosity differences between ortho- and para-dimethoxy-functionalized MOFs. Detailed
structural analysis using X-ray crystallographic data revealed significant
differences in the coordination environments of DMOF-[2,3-(OMe)2] and DMOF-[2,5-(OMe)2] (DMOF = dabco MOF, dabco
= 1,4-diazabicyclo[2.2.0]octane). The coordination bond between Zn2+ and carboxylate in the ortho-functionalized
DMOF-[2,3-(OMe)2] was more rigid than that in the para-functionalized DMOF-[2,5-(OMe)2]. Quantum-chemical
simulation also showed differences in the coordination environments
of Zn secondary building unit surrounded by methoxy-functionalized
ligands and pillar ligands. In addition, the binding energy differences
between Zn2+ and regioisomeric ligands (ortho- and para-dimethoxy-functionalized benzene-1,4-dicarboxylates)
explained the rigidity and porosity changes of the mixed MOFs upon
evacuation and perfectly matched with experimental N2 adsorption
and X-ray crystallography data.
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