Switching of Redox Properties Triggered by a Thermal Equilibrium between Closed-Shell Folded and Open-Shell Twisted Species

Thermally switchable redox properties have been reported to be due to a change in the spin state of newly designed overcrowded ethylenes, which can adopt closed-shell folded and open-shell twisted forms. In this study, tetrathienylanthraquinodimethane derivatives were designed to be in thermal equilibrium between a more stable folded form and less stable but more donating twisted diradical in solution, so that the oxidation potential can be controlled by heating/cooling. This is the first example of a switching of redox properties based on a thermally equilibrated twisted diradical, which can be more readily oxidized to the twisted dication.