Multiple stable redox states and tunable ground states via the marriage of viologens and Chichibabin's hydrocarbon.

Chichibabin's hydrocarbon and viologens are among the most famous diradicaloids and organic redox systems, respectively. However, each has its own disadvantages: the instability of the former and its charged species, and the closed-shell nature of the neutral species derived from the latter, respectively. Herein, we report that terminal borylation and central distortion of 4,4'-bipyridine allow us to readily isolate the first bis-BN-based analogues (1 and 2) of Chichibabin's hydrocarbon with three stable redox states and tunable ground states. Electrochemically, both compounds exhibit two reversible oxidation processes with wide redox ranges. One- and two-electron chemical oxidations of 1 afford the crystalline radical cation 1˙ + and dication 1 2+ , respectively. Moreover, the ground states of 1 and 2 are tunable with 1 as a closed-shell singlet and the tetramethyl-substituted 2 as an open-shell singlet, the latter of which could be thermally excited to its triplet state because of the small singlet-triplet gap.