Metal-organic frameworks (MOFs) are three-dimensional networks comprised of metal clusters, regularly spaced and adjoined by rigid organic linker molecules. MOFs have emerged as a versatile class of crystalline materials with ultra-high porosity and large specific surface areas. However, MOFs have seen limited commercial use due to poor longevity in atmospheric conditions. Polymer-MOF hybrids (polyMOFs) have been developed to circumvent this issue by adjoining carboxylate-containing linker molecules along a polymer backbone, protecting the framework from moisture contamination.<br/>This work sought to elucidate the role of connectivity in polyMOFs, especially how blocky polyMOF architectures could span across multiple crystalline domains. To that end, we synthesized a poly(2,5-dihydroxy-benzenedicarboxylate) (polyDHBDC) by sequential modification of DHBDC via Williamson ether synthesis and subsequent polymerization via acyclic diene metathesis. We confirmed the formation of a polymer by <sup>1</sup>H NMR and size-exclusion chromatography. The parent-MOF UiO-66 was fabricated and X-ray diffraction (XRD) patterns were collected to confirm appropriate crystalline structures. Future work will include the copolymerization of DHBDC in the presence of various soft α,ω-alkene-terminated oligomers and the study of copolymerization kinetics, as well as the optimization of the DHBDC polymerization conditions to form the expected polyMOFs. We anticipate that the resulting materials will afford more robust and ultimately more versatile MOF hybrids.

Synthesis and characterization of copolymers for the fabrication of novel polymer-MOF crystals

2019 Spring National Meeting

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