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. Due to the intramolecular interaction caused by π-π stacking of the xanthylium units, a considerable blue shift compared to the corresponding monocations and a two-stage one-electron reduction process were observed in the dications. Furthermore, upon electrochemical reduction of dications, the formation of biradicals via radical cation species was demonstrated by UV/Vis spectroscopy with several isosbestic points at both stages. Therefore, the cation-stacking approach is a promising way to provide novel properties due to perturbation of their molecular orbitals and to stabilize the reduced species even though they have open-shell characters.

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. After one QD unit is oxidized (trigger), steric repulsion and electronic interaction between electrophores make the neighboring QD unit adopt a twisted conformation (domino process), which facilitates the following oxidation. Thus, a domino-redox reaction was achieved for the first time by a change in the HOMO level due to a drastic change in the molecular conformation.

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-Ph4QD and p-Ph4QD 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. This Feature Article shows our milestones in creating functional redox systems, where drastic changes in structure occur upon electron transfer (dynamic redox "dyrex" behaviour).