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  • Title: Sodium-coupled electron transfer reactivity of metal-organic frameworks containing titanium clusters: the importance of cations in redox chemistry.
    Author: Saouma CT, Tsou CC, Richard S, Ameloot R, Vermoortele F, Smolders S, Bueken B, DiPasquale AG, Kaminsky W, Valdez CN, De Vos DE, Mayer JM.
    Journal: Chem Sci; 2019 Feb 07; 10(5):1322-1331. PubMed ID: 30809347.
    Abstract:
    Stoichiometric reduction reactions of two metal-organic frameworks (MOFs) by the solution reagents (M = Cr, Co) are described. The two MOFs contain clusters with Ti8O8 rings: Ti8O8(OH)4(bdc)6; bdc = terephthalate (MIL-125) and Ti8O8(OH)4(bdc-NH2)6; bdc-NH2 = 2-aminoterephthalate (NH2-MIL-125). The stoichiometry of the redox reactions was probed using solution NMR methods. The extent of reduction is greatly enhanced by the presence of Na+, which is incorporated into the bulk of the material. The roughly 1 : 1 stoichiometry of electrons and cations indicates that the storage of e- in the MOF is tightly coupled to a cation within the architecture, for charge balance.
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