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

• Published in: Crystal growth & design Vol. 20; no. 8; pp. 5338 - 5345
• Main Authors: Kim, Dopil, Ha, Hyeonbin, Kim, Youngik, Son, Younghu, Choi, Jiyoon, Park, Myung Hwan, Kim, Youngjo, Yoon, Minyoung, Kim, Hyungjun, Kim, Dongwook, Kim, Min
• Format: Journal Article
• Language: English
• Published: American Chemical Society 05-08-2020
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/acs.cgd.0c00562

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.