Significant Difference in Semiconducting Properties of Isomeric All-Acceptor Polymers Synthesized via Direct Arylation Polycondensation.

The direct arylation polycondensation (DArP) appeared as an efficient method for producing semiconducting polymers but often requires acceptor monomers with orienting or activating groups for the reactive carbon-hydrogen (C-H) bonds, which limits the choice of acceptor units. In this study, we describe a DArP for producing high-molecular-weight all-acceptor polymers composed of the acceptor monomers without any orienting or activating groups via a modified method using Pd/Cu co-catalysts. We thus obtained two isomeric all-acceptor polymers, P1 and P2, which have the same backbone and side-chains but different positions of the nitrogen atoms in the thiazole units. This subtle change significantly influences their optoelectronic, molecular packing, and charge-transport properties. P2 with a greater backbone torsion has favorable edge-on orientations and a high electron mobility μe of 2.55 cm2  V-1  s-1 . Moreover, P2-based transistors show an excellent shelf-storage stability in air even after the storage for 1 month.