Molecularly Hybridized Conduction in DPP‐Based Donor–Acceptor Copolymers toward High‐Performance Iono‐Electronics

Abstract Iono‐electronics, that is, transducing devices able to translate ionic injection into electrical output, continue to demand a variety of mixed ionic–electronic conductors (MIECs). Though polar sidechains are widely used in designing novel polymer MIECs, it remains unclear to chemists how much balance is needed between the two antagonistic modes of transport (ion permeability and electronic charge transport) to yield high‐performance materials. Here, the impact of molecularly hybridizing ion permeability and charge mobility in semiconducting polymers on their performance in electrochemical and synaptic transistors is investigated. A series of diketopyrrolopyrrole (DPP)‐based copolymers are employed to demonstrate the multifunctionality attained by controlling the density of polar sidechains along the backbone. Notably, efficient electrochemical signal transduction and reliable synaptic plasticity are demonstrated via controlled ion insertion and retention. The newly designed DPP‐based copolymers further demonstrate unprecedented thermal tolerance among organic mixed ionic–electronic conductors, a key property in the manufacturing of organic electronics.