Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 25, Pages 7632-7637Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201402006
Keywords
carbon dioxide; carboxylate ligands; metal-organic frameworks; porous materials; porphyrins
Categories
Funding
- University of Nebraska-Lincoln
- NSF through Nebraska MRSEC [DMR-0820521]
- NSF/DOE [NSF/CHE-0822838]
- DOE, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1346572] Funding Source: National Science Foundation
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Metal-organic frameworks (MOFs) are emerging microporous materials that are promising for capture and sequestration of CO2 due to their tailorable binding properties. However, it remains a grand challenge to pre-design a MOF with a precise, multivalent binding environment at the molecular level to enhance CO2 capture. Here, we report the design, synthesis, and direct X-ray crystallographic observation of a porphyrinic MOF, UNLPF-2, that contains CO2-specific single molecular traps. Assembled from an octatopic porphyrin ligand with [Co-2(COO)(4)] paddlewheel clusters, UNLPF-2 provides an appropriate distance between the coordinatively unsaturated metal centers, which serve as the ideal binding sites for in situ generated CO2. The coordination of Co-II in the porphyrin macrocycle is crucial and responsible for the formation of the required topology to trap CO2. By repeatedly releasing and recapturing CO2, UNLPL-2 also exhibits recyclability.
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