Adapting Direct Arylation Polycondensation for Arbitrary Mixed Ionic and Electronic Conductors

Abstract Direct arylation polycondensation (DArP) has been developed as a straightforward method for synthesis of conjugated polymers. However, it encounters severe incompatibility with polymer‐based organic mixed ionic and electronic conductors (OMIECs) that are essential for neuromorphic engineering and bioelectronics. Herein, we demonstrate trimethyladamantyl‐flanked N‐ heterocyclic carbene (NHC) ligands motivated DArP of OMIECs. Significant steric bulkiness of such ligands shields the catalytic palladium centers against chelating chains in OMIECs. Consequently, adamantyl NHCs modulated DArP provides a general synthetic platform for OMIECs with tailored backbone and side chain variations. Furthermore, this methodology accelerates the exploration of structure‐mixed transport correlation as well as optimization of high mobility‐volumetric capacitance OMIECs. Through these advancements, we contribute an innovative toolkit to the synthetic repertoire of mixed conducting polymers.