Tethering Effects in Oligomer-Based Metal-Organic Frameworks

Dodson, Ryan A.; Park, Junkil; Kim, Jihan; Cliffe, Matthew J.; Cohen, Seth M.

Abstract

Metal-organic frameworks (MOFs) can be constructed using conventional molecular linkers or polymeric linkers (polyMOFs), but the relationship and relative properties of these related materials remain understudied. As an intermediate between these two extremes, a library of oligomeric ligand precursors (dimers, trimers) was used to prepare a series of oligomeric-linker MOFs (oligoMOFs) based on the prototypical IRMOF-1 system. IRMOF-1 was found to be remarkably tolerant to a wide variety of oligomeric linkers, the use of which greatly enhanced the MOF yield and prevented framework interpenetration. Tether length-dependent ordering of ligand and metal cluster orientations was also observed in these oligoMOFs. Improved low-humidity stability was found in oligoIRMOF-1 samples, with surface area preservation varying as a function of tether length and a complete suppression of crystalline hydrolysis products for all oligoIRMOF-1 materials. These findings pave the way toward a better understanding of the structure-function relationships between monomeric, oligomeric, and polymeric MOFs and highlight an underutilized strategy for tuning MOF properties.

Citation

Dodson, R. A., Park, J., Kim, J., Cliffe, M. J., & Cohen, S. M. (2022). Tethering Effects in Oligomer-Based Metal-Organic Frameworks. Inorganic Chemistry, 61(31), 12063-12488. https://doi.org/10.1021/acs.inorgchem.2c01567

• Journal Article Type: Article
• Acceptance Date: Jul 13, 2022
• Online Publication Date: Jul 25, 2022
• Publication Date: Aug 8, 2022
• Deposit Date: Aug 2, 2022
• Publicly Available Date: Jul 26, 2023
• Journal: Inorganic Chemistry
• Print ISSN: 0020-1669
• Electronic ISSN: 1520-510X
• Publisher: American Chemical Society (ACS)
• Peer Reviewed: Peer Reviewed
• Volume: 61
• Issue: 31
• Pages: 12063-12488
• DOI: https://doi.org/10.1021/acs.inorgchem.2c01567
• Keywords: Inorganic Chemistry; Physical and Theoretical Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/9411110
• Publisher URL: https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c01567
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c01567