Phenyldithiafulvene-Substituted Ferrocene Derivatives as Redox-Regulated Molecular Switches

We designed a new type of redox-active molecular triad in which two electron-donating dithiafulvene (DTF) groups are connected to a central ferrocene (Fc) hinge unit through phenylene linkers. Three structural isomers of the (DTF)₂-Fc system were synthesized through Suzuki-Miyaura cross-coupling followed by phosphite-promoted olefination reactions. The molecular structures and solid-state properties of these compounds were investigated by X-ray single-crystallographic analysis. Their electronic absorption and electrochemical properties in the solution phase were examined using UV-vis spectroscopy and cyclic voltammetry. Our studies showed that these compounds possess multistage redox activities due to the presence of electron-donating DTF and Fc groups, while detailed redox behaviors are dependent on the substitution patterns and steric crowdedness of each compound. To gain deeper insight, we performed density functional theory (DFT) and molecular dynamics (MD) simulations to examine the conformational and electronic properties of these compounds in neutral and different oxidation states. Furthermore, the <i>para</i>-substituted (DTF)₂-Fc was found to show intriguing supramolecular interactions with γ-cyclodextrin.