Cation-Stacking Approach Enabling Interconversion between Bis(xanthylium) and its Reduced Species.

Cyclophane-type dications with two units of xanthylium were designed, with the expectation that intramolecular interaction between cation units could induce changes in absorption and redox behavior. The desired dications were synthesized via the macrocyclic diketone as a key intermediate, which was efficiently obtained by a stepwise etherification. X-ray and UV/Vis measurements revealed that the cyclophane-type dications adopt a stacking structure in both the crystal and solution.

Domino-Redox Reaction Induced by An Electrochemically Triggered Conformational Change.

The concept of a domino-type reaction has been applied in a wide range of fields such as synthetic organic chemistry, material engineering, and life science. To extend the domino concept to redox chemistry, we designed and synthesized a dimeric quinodimethane (QD) with a nonplanar dithiin spacer. The domino-redox properties can be activated by raising the temperature, based on a thermally equilibrated twisted conformation of QD, which has a higher HOMO level that is more readily oxidized.

Redox-active tetraaryldibenzoquinodimethanes.

Quinodimethanes (QDs) are a class of non-aromatic π-conjugated compounds that are well-known to be interconvertible scaffolds in many response systems. While parent ortho- and para-QDs (o-QD and p-QD) can be easily converted to benzocyclobutenes or oligomers/polymers by the formation of C-C bonds at α-positions, the attachment of four phenyl groups to these reactive sites makes o-PhQD and p-PhQD long-lived. We have demonstrated that further dibenzo-annulation of such tetraaryl QD units also drastically increases their stability, and many tetraarylated dibenzoquinodimethane derivatives have been developed.