This paper reports the synthesis of D-A polymers containing 1,2-dithienylethene (DTE) units via palladium-catalyzed direct arylation polymerization (DArP). The reaction of dibromoisoindigo (1-Br) and DTE (2-H), in the presence of Pd2(dba)3·CHCl3 (0.5 mol%), P(2-MeOC6H4)3 (L1) (2 mol%), pivalic acid (1 equiv) as catalyst precursors, and Cs2CO3 (3 equiv) as a base affords poly(1-alt-2) with a high molecular weight (Mn up to 44,900). Although, it has been known that monomers, with plural C–H bonds, tend to form insoluble materials via direct arylation at undesirable C–H positions; the reaction of 1-Br and 2-H cleanly proceeds without insolubilization. The resulting polymer has a well-controlled structure and exhibits good charge transfer characteristics in an organic field-effect transistor (OFET), compared to the polymer produced by Migita–Kosugi–Stille cross-coupling polymerization. The DArP product displays an ideal linear relationship in the current–voltage curve, whereas the Migita–Kosugi–Stille product shows a VG-dependent change in the charge mobility.

e r i z a t i o n o f p o l y -(thienylenevinylene) is found to be a viable fabrication method for semiconducting trans-poly(thienylenevinylene) (trans-P1) thin films. Specifically, thin films of trans-P1, an alternating copolymer containing isoindigo and (E)-1,2-dithienylethene units, which are well known as an excellent p-type semiconductor, were prepared by thermally annealing thin films of the cis-poly(thienylenevinylene) (cis-P1) isomer (92% cis) at 240 °C for 30 min. The hole mobility of the isomerized films is comparable to that of films prepared from spin-coated solutions of the trans-isomer. Taking advantage of the greater solubility of the cis-isomer, it was possible to replace the toxic halogenated solvents normally needed for the dissolution of trans-P1 with the environmentally friendly 2-MeTHF. Solid-state cis-to-trans isomerization is therefore a potentially attractive fabrication option for the commercial development of sustainable, printable electronics.