Insight from Electrochemical Analysis in the Radical Cation State of a Monopyrrolotetrathiafulvalene‐Based [2]Rotaxane

Mechanically interlocked molecules are a class of compounds used for controlling directional movement when barriers can be raised and lowered using external stimuli. Applied voltages can turn on redox states to alter electrostatic barriers but their use for directing motion requires knowledge of their impact on the kinetics. Herein, we make the first measurements on the movement of cyclobis(paraquat‐p‐phenylene) (CBPQT4+) across the radical‐cation state of monopyrrolotetrathiafulvalene (MPTTF) in a [2]rotaxane using variable scan‐rate electrochemistry. The [2]rotaxane is designed in a way that directs CBPQT4+ to a high‐energy co‐conformation upon oxidation of MPTTF to either the radical cation (MPTTF⋅+) or the dication (MPTTF2+). 1H NMR spectroscopic investigations carried out in acetonitrile at 298 K showed direct interconversion to the thermodynamically more stable ground‐state co‐conformation with CBPQT4+ moving across the oxidized MPTTF2+ electrostatic barrier. The electrochemical studies revealed that interconversion takes place by movement of CBPQT4+ across both the MPTTF•+ (19.3 kcal mol−1) and MPTTF2+ (18.7 kcal mol−1) barriers. The outcome of our studies shows that MPTTF has three accessible redox states that can be used to kinetically control the movement of the ring component in mechanically interlocked molecules. Electrochemical studies on a bistable [2]rotaxane incorporating a monopyrrolotetrathiafulvalene (MPTTF) unit (green) and an oxyphenylene (OP) moiety (red) in the dumbbell component and encircled by the cyclobis(paraquat‐p‐phenylene) (CBPQT4+) ring (blue) was used to profile the energy landscapes when the CBPQT4+ ring moves across the MPTTF unit in all of its three accessible redox states (0, +1, and +2).