Abstract
Organic redox systems that can undergo oxidative and reductive (ambipolar) electron transfer are elusive yet attractive for applications across synthetic chemistry and energy science. Specifically, the use of ambipolar redox systems in proton-coupled electron transfer (PCET) reactions is largely unexplored but could enable "switchable" reactivity wherein the uptake and release of hydrogen atoms are controlled using a redox stimulus. Here, we describe the synthesis and characterization of an ambipolar functionalized terthiophene (TTH) bearing methyl thioether and phosphine oxide groups that exhibits switchable PCET reactivity. Electrochemical studies established that the functionalized TTH can be reversibly oxidized and reduced, prompting the synthesis and characterization of cationic and anionic radicals on a single TTH platform. Combined structural, spectroscopic, and computational investigations revealed the influence of the methyl thioether and phosphine oxide moieties on the TTH electronic structure that results in the stabilization of both cationic and anionic radicals. Upon single-electron oxidation, the functionalized TTH serves as a hydrogen atom acceptor and undergoes PCET with 1,4-dihydroquinone to generate a TTH hydroxyphosphonium species. The process was found to be reversible upon single-electron reduction, with functionalized TTH acting as a hydrogen atom donor in a PCET reaction with 2,3-dimethylanthraquinone. The thermochemistry of the O-H bond formed and cleaved in functionalized TTH during the reaction sequence was investigated, revealing that a bond weakening of 30 kcal/mol underpins the switchable PCET reactivity. Overall, these studies provide an electrochemical, structural, spectroscopic, and thermochemical foundation for the use of ambipolarity to control PCET reactions in organic redox systems.