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Ligand Redox Non-innocence in the Stoichiometric Oxidation of Mn2(2,5-dioxidoterephthalate) (Mn-MOF-74)
- Source :
- Journal of the American Chemical Society. 136:3334-3337
- Publication Year :
- 2014
- Publisher :
- American Chemical Society (ACS), 2014.
-
Abstract
- Unsaturated metal sites within the nodes of metal-organic frameworks (MOFs) can be interrogated by redox reagents common to small molecule chemistry. We show, for the first time, that an analogue of the iconic M2(2,5-dioxidoterephthalate) (M2DOBDC, MOF-74) class of materials can be stoichiometrically oxidized by one electron per metal center. The reaction of Mn2DOBDC with C6H5ICl2 produces the oxidized material Cl2Mn2DOBDC, which retains crystallinity and porosity. Surprisingly, magnetic measurements, X-ray absorption, and infrared spectroscopic data indicate that the Mn ions maintain a formal oxidation state of +2, suggesting instead the oxidation of the DOBDC(4-) ligand to the quinone DOBDC(2-). These results describe the first example of ligand redox non-innocence in a MOF and a rare instance of stoichiometric electron transfer involving the metal nodes. The methods described herein offer a synthetic toolkit that will be of general use for further explorations of the redox reactivity of MOF nodes.
- Subjects :
- Models, Molecular
Chemistry
Ligand
Inorganic chemistry
Molecular Conformation
Phthalic Acids
General Chemistry
Ligands
Photochemistry
Biochemistry
Redox
Catalysis
Non-innocent ligand
Quinone
Metal
Electron transfer
Colloid and Surface Chemistry
Coordination Complexes
Oxidation state
visual_art
visual_art.visual_art_medium
Reactivity (chemistry)
Oxidation-Reduction
Subjects
Details
- ISSN :
- 15205126 and 00027863
- Volume :
- 136
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi.dedup.....fd11fac05e35b68f018e0b3487dd412c