Stabilization of Charge Carriers in Picket-Fence Polythiophenes Using Dielectric Side Chains

Insulated molecular wires (IMWs) are π-conjugated polymers that are molecularly sheathed with an insulating layer and are structurally analogous to electric power cords at the nanoscale. Such unique architectures are expected in molecular electronics and organic devices. Herein, we propose a new molecular design concept of IMWs, in which the sheaths can be customized, thereby enabling the modulation of the electronic properties of the interior π-conjugated systems. To this end, we focused our attention on the dielectric constant of the sheaths, as it governs the electrostatic interaction between charges. Upon doping, charge carriers, such as polaron and bipolaron, were generated regardless of the dielectric properties of the sheaths. Flash-photolysis time-resolved microwave conductivity measurements revealed that intrawire charge carrier mobility was independent of the sheaths. However, we found that the charge carriers could be stabilized by the sheaths with a high dielectric constant owing to the charge screening effect. We expect that IMWs designed in this way will be useful in a variety of applications, where the nature of charge carriers plays an important role, and particularly when redox switching is required (e.g., electrochromic, magnetic, and memory applications).