Ligand Redox Non-innocence in the Stoichiometric Oxidation of Mn2(2,5-dioxidoterephthalate) (Mn-MOF-74)

Anthony Cozzolino, Carl K Brozek, Ryan D Palmer, Junko Yano, Minyuan Li, Mircea Dinca

Research output: Contribution to journalArticlepeer-review

Abstract

We demonstrate that unsaturated metal sites within the nodes of metal‐organic frameworks can be inter‐ rogated by redox reagents common to small molecule chem‐ istry. 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 the hypervalent iodine reagent iodobenzene dichloride, PhICl2, requires precise control of both stoichiometry and temperature to produce the oxidized material Cl2Mn2DOBDC, which retains crystallinity and porosity. This contrasts with oxidations by Cl2 and other gaseous oxidants, which cause decomposition of the parent framework. Sur‐ prisingly, magnetic measurements, X‐ray absorption and infrared spectroscopic data show that the Mn ions maintain a formal oxidation state of +2, suggesting instead the oxidation of the DOBDC4 ligand to the quinone DOBDC2 . Control expe
Original languageEnglish
Pages (from-to)3334-3337
JournalJournal of the American Chemical Society
StatePublished - Mar 5 2014

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