Air and Moisture Stable para- and ortho-Quinodimethane Derivatives Derived from bis-N-Heterocyclic Olefins

Abstract

Herein we report the development of a new methodology for the synthesis of various quinodimethane derivatives under two-electron oxidation of bis-Nheterocyclic olefins linked by different π-conjugated aromatic spacers. In case of paraand ortho-phenylene bridge, we obtained air and moisture stable diimidazolium paraand ortho-quinodimethane derivatives. Analogues of the para-phenylene spacer such as tetrafluoro-p-phenylene and p-anthracene also led to the corresponding air and moisture stable quinodimethane derivatives. This emphasizes the influence of imidazolium substituents which facilitate the air and moisture stability of the quinodimethane derivatives. Differences were observed for the electron transfer processes: two one-electron vs one two-electron redox transitions between bis-N-heterocyclic olefins and diimidazolium-quinodimethanes depending on the employed π-conjugated aromatic spacer. The formation of the π-conjugated radical-cations, transient redox intermediates between bis-N-heterocyclic olefins and diimidazolium-quinodimethanes, was addressed by an EPR investigation.

Introducing an orthogonally polarized electron-rich alkene: synthesis of a zwitterionic boron-containing π-conjugated system

“…That a complete intramolecular charge transfer occurs in case of 8 is due to the raised electron-donor strength of the respective alkene motif in 8 ( E 1/2 = −1.45 and E 1/2 = −0.52 V vs. Fc/Fc + ) compared to VIII (anodic peak potential E pa = −0.49 V vs. Fc/Fc + ). 22…”

“…That a complete intramolecular charge transfer occurs in case of 8 is due to the raised electron-donor strength of the respective alkene motif in 8 (E 1/2 = À1.45 and E 1/2 = À0.52 V vs. Fc/Fc + ) compared to VIII (anodic peak potential E pa = À0.49 V vs. Fc/Fc + ). 22 Scheme 3 Synthesis of 8 and structural representation of VIII. In conclusion, we report the synthesis of a hitherto unknown class of alkenes which is concurrently electron-rich, twisted, and push-pulling in nature.…”