Mesopolymer synthesis by ligand-modulated direct arylation polycondensation towards n-type and ambipolar conjugated systems

Conjugated polymers are attractive components for plastic electronics, but their structural defects, low solubility and batch-to-batch variation—mainly in terms of molecular weight and

dispersity—hinder practical applications. Here, we demonstrate that these issues can be circumvented by using conjugated mesopolymers, which have the advantages of both oligomers and

polymers. A diketopyrrolopyrrole monomer and a benzothiadiazole derivative react through direct arylation polycondensation, promoted by sterically hindered adamantyl ligand coordinated

palladium catalysts, to form mesopolymers. The reaction is facile, environmentally benign (it does not require tin or boron reagents) and occurs in high yields. The resulting mesopolymers

have a strictly alternating donor–acceptor structure, without detectable homocoupling and β-arylation defects, and exhibit number-averaged molecular weights (Mn) between 1 and 10 kDa. They

also show good solution processability and have significantly enhanced electron mobilities, which makes them n-type and ambipolar semiconductors, with advantages over their polymer

counterparts.

All relevant data supporting the findings of this study are available in this paper and its Supplementary Information. Synthetic procedures and characterization for all the new compounds,

description of the computational study and all copies of NMR spectra and GPC traces are provided in the Supplementary Information. All data are available from the corresponding author upon

reasonable request.

The authors thank A. Tenaglia for his suggestions. The authors acknowledge financial support from the Ministry of Science and Technology of China (2016YFB0401100 and 2017YFA0204503), the

National Natural Science Foundation of China (51725304, 51633006, 51703159, 51733004, 91433115 and 21875158), the Strategic Priority Research Program (XDB12030300 and XDB 12000000) of the

Chinese Academy of Sciences, the Youth Innovation Promotion Association of the Chinese Academy of Sciences and the National Program for Support of Top-notch Young Professionals.

The authors contributed equally: Zhenjie Ni, Hanlin Wang and Huanli Dong.

Beijing National laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

Zhenjie Ni, Hanlin Wang, Huanli Dong, Qiang Zhao & Wenping Hu

Tianjin Key Laboratory of Molecular Optoelectronic Sciences, School of Science, Tianjin University, Tianjin, China

Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, China

W.H. conceived the work. Z.N. performed the synthetic experiments and characterization. H.W. and Q.Z. performed the device fabrication and analysis. Y.D. performed the computational study,

X.Z. provided several monomers. H.D. directed the synthesis and device fabrication. Z.N. and H.W. wrote the manuscript. W.H. provided overall supervision.

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Synthetic procedures; Characterization, including NMR spectra and GPC traces; Computational details

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