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Tethering Effects in Oligomer-Based Metal-Organic Frameworks

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

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Ryan A. Dodson

Junkil Park

Jihan Kim

Seth M. Cohen


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.

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
Keywords Inorganic Chemistry; Physical and Theoretical Chemistry
Public URL
Publisher URL
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


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