Thiophene–Vinylene–Thiophene-Based Donor–Acceptor Copolymers with Acetylene-Inserted Branched Alkyl Side Chains To Achieve High Field-Effect Mobilities

2-Alkyl(1)alkyl(2)-type aliphatic side chains with a branching point position at the C2-position (such as 2-ethylhexyl or 2-octayldodecyl) have been widely implanted into numerous donor–acceptor conjugated copolymers for solution processable transistors or organic solar cells. However, the tertiary branching site located at the second carbon inevitably imposes steric hindrance that twists the main-chain coplanarity and attenuates interchain interactions. In this research, we developed a new two-dimensonal thiophene–vinylene–thiophene (TVT) derivative where a carbon–carbon triple bond is inserted between the thiophene unit and the 2-octyldodecyl group. This acetylene-incorporated TVT (aTVT) was copolymerized with 5,10-di­(thiophen-2-yl)­naphtho­[1,2-c:5,6-c′]­bis­([1,2,5]­thiadiazole) (DTNT) and 5,6-difluoro-4,7-di­(thiophen-2-yl)­benzo­[c]­[1,2,5]­thiadiazole (DTFBT) to form the polymers PaTVT-NT and PaTVT-FBT, respectively. PTVT-FBT, without the triple bond, was also prepared for comparison. The insertion of a linear triple bond moves the tertiary carbon away from the main chain to reduce the steric hindrance, thereby improving the main-chain coplanarity and facilitating the interchain interactions. The acetylene-incorporated copolymers show better thermal stability, red-shifted absorption spectra, stronger intermolecular aggregation, lower-lying electron affinity, and much higher solid-state crystallinity. Due to the linear and coplanar polymeric backbone supported by theoretical calculation, PaTVT-NT exhibits high crystallinity and adopts strong stacking with an edge-on orientation in the thin film evidenced by 2D-GIXRD, leading to a high p-type OFET mobility up to 1.27 cm2 V–1 s–1 with an on–off ratio of 9.22 × 105. This value represents the highest value among the NT-based polymers. PaTVT-FBT also achieved a high mobility of 0.78 cm2 V–1 s–1, which greatly outperforms the corresponding nonacetylene PTVT-FBT counterpart. Most importantly, the preparation of 2-alkyl(1)alkyl(2)–acetylenyl side chain is synthetically feasible, which can be easily applied to create new conjugated polymers for high-performance solution-processable optoelectronics