Postsynthetic polymer-ligand exchange hybridization in M-MOF-74 composites

Pastore, Vincent J.; Sullivan, Meghan G.; Rzayev, Javid; Cook, Timothy R.

doi:10.1080/00958972.2021.1876852

Cited by 3 publications

(1 citation statement)

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“…Ligand exchange is a synthetic method commonly employed in the MOF community to correct defects within frameworks, to add surface functionality to nanoparticles, and to make cross-linked composite materials. − UiO-66, a Zr-based MOF, is shown to undergo postsynthetic ligand exchange at room temperature, − yet ligand exchange has not been explored for ZrMOPs as a synthetic route or a postsynthetic modification method.…”

Section: Introductionmentioning

confidence: 99%

Phase-Pure Zirconium Metal–Organic Polyhedra Enabled by a Ligand Substitution Strategy

Sullivan,

Welgama,

Crawley

et al. 2023

Chem. Mater.

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Zirconium-based metal−organic polyhedra (ZrMOPs) are attractive due to their high stabilities, low-cost building blocks, and solubilities relative to their metal−organic framework analogues (e.g., UiO-66); although these sorts of selfassembled cages often form single thermodynamic products, ZrMOP architectures are typically plagued by the formation of both V 4 L 6 "tetrahedra" and V 2 L 3 "lanterns" (V = vertex, L = ligand) as coproducts of their syntheses. In this work, we demonstrate a ligandexchange strategy to isolate previously inaccessible phase-pure ZrMOPs using two different dicarboxylate donors. We also describe characterization methods that can be used to discriminate between the two architectures to confirm our approach provides synthetic selectivity. The phase-pure materials were found to have drastically different Brunauer−Emmett−Teller (BET) areas, with lanterns exhibiting significantly smaller surface areas (4−20 m 2 /g) than the tetrahedral architectures (393−605 m 2 /g), irrespective of counterions or bridging dicarboxylates. By obviating mixed-phase products of synthesis, our generalizable ligand-exchange pathway to phase-pure ZrMOPs enables systematic fundamental studies and will advance the functional use of these materials.

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