Solvent-Driven Dynamics: Crafting Tailored Transformations of Cu(II)-Based MOFs

Abstract

Metal−organic frameworks (MOFs), a sort of crystalline porous coordination polymers composed of metal ions and organic linkers, have been intensively studied for their ability to take up nonpolar gas-phase molecules such as ethane and ethylene. In this context, interpenetrated MOFs, where multiple framework nets are entwined, have been considered promising materials for capturing nonpolar molecules due to their relatively higher stability and smaller micropores. This study explores a solvent-assisted reversible strategy to interpenetrate and deinterpenetrate a Cu(II)-based MOF, namely, MOF-143 (noninterpenetrated form) and MOF-14 (doubly interpenetrated forms). Interpenetration was achieved using protic solvents with small molecular sizes such as water, methanol, and ethanol, while deinterpenetration was accomplished with a Lewis-basic solvent, pyridine. Additionally, this study investigates the adsorptive separation of ethane and ethylene, which is a significant application in the chemical industry. The results showed that interpenetrated MOF-14 exhibited higher ethane and ethylene uptakes compared to the noninterpenetrated MOF-143 due to narrower micropores. Furthermore, we demonstrate that pristine MOF-14 displayed higher ethane selectivity than transformed MOF-14 from MOF-143 by identifying the "fraction of micropore volume" as a key factor influencing ethane uptake. These findings highlight the potential of controlled transformations between interpenetrated and noninterpenetrated MOFs, anticipating that larger MOF crystals with narrower micropores and higher crystallinity will be more suitable for selective gas capture and separation applications.

Magnetic and Porous Regulation in Cobalt(II) Hydrogen-Bonded Organic Framework via Supramolecular Isomerism

“…These isomers serve as intriguing molecular systems for studying structure–property relationships and unveiling the self-assembly processes of supramolecular materials. , This intriguing phenomenon has garnered widespread attention. To date, various types of isomerism, such as supramolecular isomerism, interpenetration isomerism, , and topological isomerism, have been observed in different types of crystalline porous materials. However, although a variety of MOF isomers have been reported, supramolecular framework isomers originating from distinct supramolecular interactions, such as HOF isomers, are extremely rare.…”

Functionalized Metal–Organic Framework with Azo Double and Amide Groups for Highly Efficient Iodine Capture

“…Metal–organic frameworks (MOFs) are an emerging kind of porous materials that have found wide-ranging applications in gas separation, toxic waste removal, and catalysis for their large surface area, modifiable structures, and excellent stability. − In recent years, many MOFs have been applied to research I 2 adsorption, such as MIL-53-NH 2 (Al), ZIF-8, UiO-66-PYDC, [(ZnI 2 ) 3 (TPT) 2 ], suggesting that MOFs have a potential role in removing nuclear waste. Nevertheless, the development of MOFs with efficient I 2 capture properties remains a huge challenge.…”

Dual modifications of sensitizers and lanthanide ions on a two-dimensional zirconium-based metal–organic framework for photoluminescent detection

“…1,2 Furthermore, the use of organic sensitizers to render energy transfer to the adjacent lanthanide, also known as the “antenna effect”, can remarkably amplify the photoluminescent (PL) properties of lanthanide ions. 1,2 On the other hand, metal–organic frameworks (MOFs) are porous materials constructed from metal-ion clusters and organic linkers with high specific surface areas, interconnected pore structures and modulable chemical functionality, 3–8 which have been widely explored as active materials for a range of catalytic applications, 9–15 ionic conductors 16 and chemical sensors. 17–21 Spatially separated active sites immobilized within the highly porous scaffold are expected to be highly accessible to the reactants or analytes coming from the external environment, and the MOF in the form of solid is more easily recycled after use compared to those soluble luminescent materials.…”