Cation exchange in metal-organic frameworks (MOFs): The hard-soft acidbase (HSAB) principle appraisal

Hamisu, Aliyu M. and Ariffin, Azhar and Wibowo, Arief C. (2020) Cation exchange in metal-organic frameworks (MOFs): The hard-soft acidbase (HSAB) principle appraisal. Inorganica Chimica Acta, 511. ISSN 0020-1693, DOI

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Cation exchange in Metal-Organic Frameworks (MOFs) is an emerging synthetic pathway for modifying che-mical compositions and has been expansively investigated. It has been shown to be an important tool for leveraging novel functional MOFs that otherwise have not been achieved via the conventional technique. Yet, the governing physical and chemical factors responsible for this occurrence are not clearly understood. The most encountered interpretations are related with the presence of open metal sites, coordinated solvent or lattice distortion tolerance. There is no unifying concept that gives a detailed insight on some common observations in cation exchanged MOFs, e.g. why some MOFs can undergo complete and reversible cation exchange, complete but irreversible, partial exchange, and in some cases, they do not exchange. Other puzzles include, why certain cation can exchange others while some cannot, why exchange can proceed in certain solvents but fails in others. Herein, we qualitatively demonstrate how the concept of Hard-Soft Acid-Base principle allows a plethora of reported experimental observations dealing with cation exchange at the SBUs of MOFs could be reasonably explained. This review is intended to provide rationalization of cation exchange behaviors in both stable and labile MOFs, based on the hardness or softness of cations and ligands, effect of solvents, temperature and ex-change period using the HSAB principle's point of view. We hope that this review may lead to a deeper un-derstanding of the cation exchange behavior in MOFs, which in turns allow chemists to use it as a predictive tool for engineering novel functional MOFs with the required complexities.

Item Type: Article
Uncontrolled Keywords: Full or partial cation exchange; Reversible or irreversible cation exchange; HSAB principle; Stable MOFs; Labile MOFs
Subjects: Q Science > Q Science (General)
Q Science > QD Chemistry
Divisions: Faculty of Science
Faculty of Science > Department of Chemistry
Depositing User: Ms Zaharah Ramly
Date Deposited: 29 Nov 2023 14:35
Last Modified: 29 Nov 2023 14:35

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