Wireless Electrochemical Actuation of Conducting Polymers

Electrochemical actuation of conducting polymers usually requires a direct connection to an electric power supply. In this contribution, we suggest to overcome this issue by using the concept of bipolar electrochemistry. This allows changing the oxidation state of the polymer in a gradual and wireless way. Free‐standing polypyrrole films were synthesized with an intrinsic morphological asymmetry of their two faces in order to form a bilayer structure. Immersing such objects in an electrolyte solution and exposing them to a potential gradient leads to the asymmetric oxidation/reduction of the polymer, resulting in differential shrinking and swelling along the main axis. This additional asymmetry is responsible for a structural deformation. Optimization allowed highly efficient bending, which is expected to open up completely new directions in the field of actuation due to the wireless mode of action.     

Selenium‐Substituted Diketopyrrolopyrrole Polymer for High‐Performance p‐Type Organic Thermoelectric Materials

Development of high‐performance organic thermoelectric (TE) materials is of vital importance for flexible power generation and solid‐cooling applications. Demonstrated here is the significant enhancement in TE performance of selenium‐substituted diketopyrrolopyrrole (DPP) derivatives. Along with strong intermolecular interactions and high Hall mobilities of 1.0–2.3 cm² V^?1 s^?1 in doping‐states for polymers, PDPPSe‐12 exhibits a maximum power factor and ZT of up to 364 μW m^?1 K^?2 and 0.25, respectively. The performance is more than twice that of the sulfur‐based DPP derivative and represents the highest value for p‐type organic thermoelectric materials based on high‐mobility polymers. These results reveal that selenium substitution can serve as a powerful strategy towards rationally designed thermoelectric polymers with state‐of‐the‐art performances.     

ipso‐Arylative Ring‐Opening Polymerization as a Route to Electron‐Deficient Conjugated Polymers

ipso‐Arylative ring‐opening polymerization of 2‐bromo‐8‐aryl‐8H‐indeno[2,1‐b]thiophen‐8‐ol monomers proceeds to M_n up to 9 kg mol^?1 with conversion of the monomer diarylcarbinol groups to pendent conjugated aroylphenyl side chains (2‐benzoylphenyl or 2‐(4‐hexylbenzoyl)phenyl), which influence the optical and electronic properties of the resulting polythiophenes. Poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to have lower frontier orbital energy levels (HOMO/LUMO=?5.9/?4.0 eV) than poly(3‐hexylthiophene) owing to the electron‐withdrawing ability of the aryl ketone side chains. The electron mobility (ca. 2×10^?3 cm² V^?1 s^?1) for poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to be significantly higher than the hole mobility (ca. 8×10^?6 cm² V^?1 s^?1), which suggests such polymers are candidates for n‐type organic semiconductors. Density functional theory calculations suggest that backbone distortion resulting from side‐chain steric interactions could be a key factor influencing charge mobilities.