Three unsymmetrical diiodobichalcogenophenes SSeI2, STeI2, and SeTeI2 and a diiodoterchalcogenophene SSeTeI2 were prepared to synthesize a new class of polychalcogenophenes with precisely controlled sequences by catalyst-transfer polycondensation.

A TT-terminal ladder-type donor is generally a better molecular design than the corresponding T-terminal ladder-type isomer for the development of new A–D–A NFEAs.

2-Alkyl (1) alkyl (2) -type aliphatic side chains with a branching point position at the C 2 -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 cm 2 V −1 s −1 with an on−off ratio of 9.22 × 10 5 . This value represents the highest value among the NT-based polymers. PaTVT-FBT also achieved a high mobility of 0.78 cm 2 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.

In this research, we developed six new selenophene-incorporated naphthobisthiadiazole-based donor−acceptor polymers PNT2Th2Se-OD, PNT2Se2Th-OD, PNT4Se-OD, PNT2Th2Se-DT, PNT2Se2Th-DT, and PNT4Se-DT. The structure−property relationships have been systematically established through the comparison of their structural variations: (1) isomeric biselenophene/bithiophene arrangement between PNT2Th2Se and PNT2Se2Th polymers, (2) biselenophene/bithiophene and quarterselenophene donor units between PNT2Th2Se/PNT2Se2Th and PNT4Se polymers, and (3) side-chain modification between the 2octyldodecylthiophene (OD)-and 2-decyltetradecyl (DT)-series polymers. The incorporation of selenophene units in the copolymers induces stronger charge transfer to improve the light-harvesting capability while maintaining the strong intermolecular interactions to preserve the intrinsic crystallinity for high carrier mobility. The organic field-effect transistor device using PNT2Th2Se-OD achieved a high hole mobility of 0.36 cm 2 V −1 s −1 with an on/off ratio of 1.9 × 10 5 . The solar cells with PNT2Th2Se-OD:PC 71 BM exhibited a power conversion efficiency of 9.47% with a V oc of 0.68 V, an fill factor of 67%, and an impressive J sc of 20.69 mA cm −2 .

This work clearly demonstrates the importance of chemical planarization in designing high-performance nonfullerene acceptors and the ternary-blend device using PBDB-T:DTFT9-FIC:PC71BM achieved a high PCE of 11.82%.