Stepwise Operation of a Molecular Rotary Motor Driven by an Appel Reaction.

To date, only a small number of chemistries and chemical fueling strategies have been successfully used to operate artificial molecular motors. Here, we report the 360° directionally biased rotation of phenyl groups about a C-C bond, driven by a stepwise Appel reaction sequence. The motor molecule consists of a biaryl-embedded phosphine oxide and phenol, in which full rotation around the biaryl bond is blocked by the P-O oxygen atom on the rotor being too bulky to pass the oxygen atom on the stator. Treatment with SOCl2 forms a cyclic oxyphosphonium salt (removing the oxygen atom of the phosphine oxide), temporarily linking the rotor with the stator. Conformational exchange via ring flipping then allows the rotor and stator to twist back and forth past the previous limit of rotation. Subsequently, the ring opening of the tethered intermediate with a chiral alcohol occurs preferentially through a nucleophilic attack on one face. Thus, the original phosphine oxide is reformed with net directional rotation about the biaryl bond over the course of the two-step reaction sequence. Each repetition of SOCl2-chiral alcohol additions generates another directionally biased rotation. Using the same reaction sequence on a derivative of the motor molecule that forms atropisomers rather than fully rotating 360° results in enantioenrichment, suggesting that, on average, the motor molecule rotates in the "wrong" direction once every three fueling cycles. The interconversion of phosphine oxides and cyclic oxyphosphonium groups to form temporary tethers that enable a rotational barrier to be overcome directionally adds to the strategies available for generating chemically fueled kinetic asymmetry in molecular systems.

The Influence of Strain on the Rotation of an Artificial Molecular Motor.

In artificial small-molecule machines, molecular motors can be used to perform work on coupled systems by applying a mechanical load-such as strain-that allows for energy transduction. Here, we report how ring strain influences the rotation of a rotary molecular motor. Bridging the two halves of the motor with alkyl tethers of varying sizes yields macrocycles that constrain the motor's movement. Increasing the ring size by two methylene increments increases the mobility of the motor stepwise and allows for fine-tuning of strain in the system. Small macrocycles (8-14 methylene units) only undergo a photochemical E/Z isomerization. Larger macrocycles (16-22 methylene units) can perform a full rotational cycle, but thermal helix inversion is strongly dependent on the ring size. This study provides systematic and quantitative insight into the behavior of molecular motors under a mechanical load, paving the way for the development of complex coupled nanomachinery.