Diverse redox-mediated transformations to realize the para-quinoid, σ-bond, and ortho-diphenoquinoid forms.

Abstract

π-Electron systems with multiple redox-active units have attracted attention in various fields due to their potential applications. However, the design strategy remains elusive to selectively synthesize the diverse molecular structures of redox-convertible species. In this study, covalently linked quinodimethane derivatives with a sulfur bridge [(Ar₄QD)₂S] were designed as redox-active motifs that can be converted into three different geometries via redox reaction. Here we show that the favored geometry of the corresponding redox states of (Ar₄QD)₂S can be precisely controlled by adjusting the steric bulk of the substituents on the aryl group to change the proximity of the quinodimethane units. Notably, this redox-mediated strategy also leads to the isolation and structural determination of the missing link with an o-diphenoquinoid structure, a diphenoquinoid isomer whose isolation had remained elusive for almost a century. Thus, this study provides a method that allows the modulation/control of electronically and/or thermodynamically stable structures, as well as their electronic and spectroscopic properties.