We report a new class of redox-­‐active vertex-­‐differentiated dodecaborate clusters featuring pentafluoroaryl groups. These [B12(OR)11NO2] clusters share several unique photophysical properties with their [B12(OR)12] analogues, while exhibiting significantly higher (+0.5 V) redox potentials. This work describes the synthesis, characterization, and isolation of [B12(O-­‐CH2C6F5)11NO2] clusters in all 3 oxidation states (dianion, radical, and neutral). Reactivity to post-­‐functionalization with thiol species via SNAr on the pentafluoroaryl groups is also demonstated.

We report a new class of redox-­‐active vertex-­‐differentiated dodecaborate clusters featuring pentafluoroaryl groups. These [B12(OR)11NO2] clusters share several unique photophysical properties with their [B12(OR)12] analogues, while exhibiting significantly higher (+0.5 V) redox potentials. This work describes the synthesis, characterization, and isolation of [B12(O-­‐CH2C6F5)11NO2] clusters in all 3 oxidation states (dianion, radical, and neutral). Reactivity to post-­‐functionalization with thiol species via SNAr on the pentafluoroaryl groups is also demonstated.