α-Diimine Ligand Modulated Direct Arylation Polycondensation for Ultrahigh μC* Organic Mixed Conductors

Abstract Direct arylation polycondensation (DArP) has attracted extensive attention due to its simplified procedures and reduced chemical wastes in polymer synthesis. However, DArP for organic mixed ionic-electronic conductors (OMIECs) has remained a challenge due to scarcity of efficient ligands. Existing ligands, phosphines display inferior reactivity towards oligo(ethylene) glycol (OEG)-functionalised monomers due to competing coordination. Herein, to address this challenge, we innovate α-diimine modulated DArP, employing ligands that are readily synthesized by condensation of simple aromatic amines with glyoxal. The α-diimine ligands exhibit high catalytic reactivity in the DArP of OMIECs with a variety of chalconophenes, irrespective of their degree of aromaticity and electron density achieving yields over 80% and molecular weights higher than established DArP. More importantly, the realistic applicability of our α-diimine modulated DArP was validated by a furan-thiophene flanked, unsymmetric OMIEC was synthesized to exhibit a remarkable transconductance of 8.2 mS and a μC* value of 702.6 F cm−1 V−1 s−1. These results establish our α-diimine-Pd system as a robust platform for exploring electrochemically active conjugated polymers.