Assembled Structures of Anion-Responsive π‑Systems Tunable by Alkyl/Perfluoroalkyl Segments in Peripheral Side Chains

Anion-responsive π-conjugated molecules carrying semifluoroalkyl chains were newly synthesized to examine the self-assembling features and resulting electronic properties of these molecules and of ion-pairing complexes formed when combined with a planar cation salt. Although these compounds self-organize into columnar mesophases similar to that of their hydrocarbon analog, in both the charge-free and charge-based states, the fluorous moieties appended to the π-conjugated units change the detailed phase-transition profiles and improve the thermal stability of the ion-pairing complexes. The length of the fluoroalkyl chains at the termini strongly affects the charge carrier mobility through the one-dimensionally arranged π-conjugated motifs, giving highly mobile charge carriers with extremely high intrinsic mobility of 1.1 cm2 V–1 s–1 as a maximum value.