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Saouma, Caroline T. ; Tsou, Chih-Chin ; Richard, Sarah ; Ameloot, Rob ; Vermoortele, Frederik ; Smolders, Simon ; Bueken, Bart ; DiPasquale, Antonio G. ; Kaminsky, Werner ; Valdez, Carolyn N. ; et al ( , Chemical Science)Stoichiometric reduction reactions of two metal–organic frameworks (MOFs) by the solution reagents (M = Cr, Co) are described. The two MOFs contain clusters with Ti 8 O 8 rings: Ti 8 O 8 (OH) 4 (bdc) 6 ; bdc = terephthalate (MIL-125) and Ti 8 O 8 (OH) 4 (bdc-NH 2 ) 6 ; bdc-NH 2 = 2-aminoterephthalate (NH 2 -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.more » « less
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Van Humbeck, Jeffrey F. ; Aubrey, Michael L. ; Alsbaiee, Alaaeddin ; Ameloot, Rob ; Coates, Geoffrey W. ; Dichtel, William R. ; Long, Jeffrey R. ( , Chem. Sci.)