Experimental, Structural, and Computational Investigation of Mixed Metal-Organic Frameworks from Regioisomeric Ligands for Porosity Control

Dopil Kim, Hyeonbin Ha, Youngik Kim, Younghu Son, Jiyoon Choi, Myung Hwan Park, Youngjo Kim, Minyoung Yoon, Hyungjun Kim, Dongwook Kim, Min Kim

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

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- A nd 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- A nd 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.

Original languageEnglish
Pages (from-to)5338-5345
Number of pages8
JournalCrystal Growth and Design
Volume20
Issue number8
DOIs
StatePublished - 5 Aug 2020

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