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DOE OSTI · 1922338

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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Abstract

Metal–organic frameworks (MOFs) can be con- structed 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. Furthermore, 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.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYDiffractionLigandsMaterialsMetal organic frameworksOligomers

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Dodson, Ryan A., Park, Junkil, Kim, Jihan, Cliffe, Matthew J., Cohen, Seth M.. 2022-07-26. Tethering Effects in Oligomer-Based Metal–Organic Frameworks. https://doi.org/10.1021/acs.inorgchem.2c01567

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