Towards Redox-Driven Unidirectional Molecular Motion.

Redox-driven molecular motion is an attractive alternative to light-driven processes. Here, the ability of an overcrowded alkene-based unimolecular light-driven rotary motor (A) to be driven by oxidation/reduction cycles is explored. We show that two-electron oxidation of A is followed by irreversible deprotonation and reduction to form a monocationic species D(+) , in which the stereogenic center is lost. This latter species was isolated through preparative electrolysis and its structure was confirmed by using single-crystal X-ray analysis. However, at short timescales and in the absence of Brønsted acids, these processes can be outrun and the oxidation of A to a dicationic species B(2+) occurs, in which the central double bond (the axle of the molecular motor) becomes a single bond; when followed by rapid reduction, it results in the reformation of A, potentially in both its stable and unstable conformations. The latter conformation, if formed, undergoes thermal helix inversion, completing a rotary cycle. The data obtained regarding these reactions provide a window of opportunity for the motor to be driven electrochemically, without degradation from chemical reactions of the oxidized motor.