Role of Side-Chain Free Volume on the Electrochemical Behavior of Poly(propylenedioxythiophenes)

Mixed ionic/electronic conducting polymers are versatile systems for, e.g., energy storage, heat management (exploiting electrochromism), and biosensing, all of which require electrochemical doping, i.e., the electrochemical oxidation or reduction of their macromolecular backbones. Electrochemical doping is achieved via electro-injection of charges (i.e., electronic carriers), stabilized via migration of counterions from a supporting electrolyte. Since the choice of the polymer side-chain functionalization influences electrolyte and/or ion sorption and desorption, it in turn affects redox properties, and, thus, electrochemically induced mixed conduction. However, our understanding of how side-chain versus backbone design can increase ion flow while retaining high electronic transport remains limited. Hence, heuristic design approaches have typically been followed. Herein, we consider the redox and swelling behavior of three poly(propylenedioxythiophene) derivatives, P(ProDOT)s, substituted with different side-chain motifs, and demonstrate that passive swelling is controlled by the surface polarity of P(ProDOT) films. In contrast, active swelling under operando conditions (i.e., under an applied bias) is dictated by the local side-chain free volume on the length scale of a monomer unit. Such insights deliver important design criteria toward durable soft electrochemical systems for diverse energy and biosensing platforms and new understanding into electrochemical conditioning ("break-in") in many conducting polymers.