Main group systems capable of undergoing controlled redox events at extreme potentials are elusive yet highly desirable for a range of organic electronics applications including use as energy storage media. Herein we describe phosphine oxide-functionalized terthiophenes that exhibit two reversible 1e reductions at potentials below -2 V vs Fc/Fc (Fc=ferrocene) while retaining high degrees of stability. A phosphine oxide-functionalized terthiophene radical anion was synthesized in which the redox-responsive nature of the platform was established using combined structural, spectroscopic, and computational characterization. Straightforward structural modification led to the identification of a derivative that exhibits exceptional stability during bulk 2 e galvanostatic charge-discharge cycling and enabled characterization of a 2 e redox series. A new multi-electron redox system class is hence disclosed that expands the electrochemical cell potential range achievable with main group electrolytes without compromising stability.
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