Tuning the electrochemical potential of perfunctionalized dodecaborate clusters through vertex differentiation

Abstract

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 S_NAr on the pentafluoroaryl groups is also demonstrated.