The development of high-performance unipolar n-type semiconducting polymers still remains a significant challenge. Only a few examples exhibit a unipolar electron mobility over 5 cm2 V–1 s–1. In this study, a series of new poly­(benzothiadiazole-naphthalenediimide) derivatives with a high unipolar electron mobility (μe) up to 7.16 cm2 V–1 s–1 in thin-film transistors are reported. The dramatically increased μe is achieved by finely optimizing the coplanar backbone conformation through the introduction of vinylene bridges, which can form intramolecular hydrogen bonds with the neighboring fluorine and oxygen atoms. The hydrogen-bonding functionalities are fused to the backbone to ensure a much more planar conformation of the conjugated π-system, as demonstrated by the density functional theory (DFT)-based calculations. The theoretical prediction is in good agreement with the experimental results. As the coplanarity is promoted by the hydrogen bonding, the thin-film crystallinity and molecular packing strength are also improved, which is evidenced by the synchrotron two-dimensional grazing-incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM) measurements. Notably, the GIWAXS measurements reveal an extremely short π–π stacking distance of 3.40 Å. Overall, this study marks a significant advance in the unipolar n-type semiconducting polymers and offers a general approach for further increasing the electron mobility of semiconducting polymers in organic electronics.

High‐mobility semiconducting polymers composed of arylene vinylene and dithiophene‐thiadiazolobenzotriazole (SN) units are developed by three powerful design strategies, namely, backbone engineering, heteroatom substitution, and side‐chain engineering. First, starting from the quaterthiophene‐SN copolymer, a vinylene spacer is inserted into the quaterthiophene unit for constructing highly‐planar backbones. Second, heteroatoms (O and N atoms) are incorporated into the thienylene vinylene moieties to tune the electronic properties and intermolecular interactions. Third, the alkyl side chains are optimized to tune the solubility and self‐assembly properties. As a consequence, a remarkable thin film transistor performance is obtained. The very high hole mobility of 3.22 cm2 V−1 s−1 is achieved for the p‐type polymer, PSNVT‐DTC8, which is the highest value ever reported for the polymers based on the benzobisthiadiazole and its analogs. Moreover, heteroatom substitution efficiently varies the charge polarity of the polymers as in the case of the N atom substituted PSNVTz‐DTC16 displaying n‐type dominant ambipolar properties with the electron mobility of 0.16 cm2 V−1 s−1. Further studies using grazing‐incidence wide‐angle X‐ray scattering and atomic force microscopy have revealed the high crystallinities of the polymer thin films with strong π–π interactions and suitable polymer packing orientations.

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,w hichl imits the choice of acceptor units.I nt his study, we describe aD ArP for producing high-molecular-weight allacceptor polymers composed of the acceptor monomers without any orienting or activating groups via am odified method using Pd/Cu co-catalysts.W et hus obtained two isomeric all-acceptor polymers,P 1a nd P2, which have the same backbone and side-chains but different positions of the nitrogen atoms in the thiazole units.T his subtle change significantly influences their optoelectronic,m olecular packing, and charge-transport properties.P 2w ith ag reater backbone torsion has favorable edge-on orientations and ah igh electron mobility m e of 2.55 cm 2 V À1 s À1 .M oreover,P 2-based transistors show an excellent shelf-storage stability in air even after the storage for 1month.

The structure of human translin at 2.2 A resolution is reported in space group C222(1). Translin forms a tetramer in the asymmetric unit. Although the monomer structure is almost the same as the crystal structure of murine translin in space group P2(1)2(1)2, the relative positions of the tetramers differ between the human and murine translins. This suggests that the multimerization of translin is flexible; the flexibility may be related to the binding to DNA/RNA.

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