3,4-Ethylenedioxythiophene-Based Isomer-Free Quinoidal Building Block and Conjugated Polymers for Organic Field-Effect Transistors

Abstract

Since quinoidal molecules have double-bond linkages between aromatic rings, they have many advantages for efficient charge transport resulting from high planarity and extended π-conjugation length. However, they unavoidably generate some isomers, which cause difficulty in purification and characterization. In this study, sulfur–oxygen conformation locking and steric repulsion approach is introduced to manipulate syn- and anti-isomerization of a quinoidal building block (bis-QEDOT). As a result, isomer-free bis-QEDOT is synthesized by introducing the 3,4-ethylenedioxy group, and the geometrical structure of bis-QEDOT is identified by thin-layer chromatography, 1H NMR, and density functional theory calculation. Furthermore, thiophene (T), bithiophene (2T), and thienylene vinylene (TV) as π-conjugated building blocks are polymerized with bis-QEDOT. Due to the quinoid structure, PQEDOT-T, PQEDOT-2T, and PQEDOT-TV show an intensified near-IR absorption and a low band gap around ∼1.16 eV. Grazing incidence wide-angle X-ray diffraction reveals that three quinoidal polymers show in the (h00) diffraction peaks up to third order after thermal annealing at 250 °C, demonstrating high crystallinity of the films. Finally, the electrical properties of the three polymers are investigated as an active layer in organic field-effect transistors showing hole mobilities of 4.3 × 10–2 (PQEDOT-T), 1.8 × 10–2 (PQEDOT-2T), and 7.8 × 10–3 cm2 V–1 s–1 (PQEDOT-TV).