We report the isolation of vanadium(II) in a metal-organic framework (MOF) by the reaction of the chloride-capped secondary building unit in the all-vanadium(III) V-MIL-101 () with 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine. The reduced material, , has a secondary building unit with the formal composition [VV], with each metal ion presenting one open coordination site. Subsequent reaction with O yields a side-on η vanadium-superoxo species, . The MOF featuring V(III)-superoxo moieties exhibits a mild enhancement in the isosteric enthalpy of adsorption for methane compared to the parent V-MIL-101. We present this synthetic methodology as a potentially broad way to access low-valent open metal sites within MOFs without causing a loss of crystallinity or porosity. The low-valent sites can serve as isolable intermediates to access species otherwise inaccessible by direct synthesis.
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