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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.

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Fig. 1: Optimization of DArP for the synthesis of mesopolymers.
Fig. 2: Defect analysis of meso-DPPBTz.
Fig. 3: Physical properties of meso-DPPBTz.
Fig. 4: OFET characteristics of meso-DPPBTz and poly-DPPBTz.

Data availability

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.


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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.

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Authors and Affiliations



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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Correspondence to Wenping Hu.

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Supplementary information

Supplementary Information

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

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Ni, Z., Wang, H., Dong, H. et al. Mesopolymer synthesis by ligand-modulated direct arylation polycondensation towards n-type and ambipolar conjugated systems. Nature Chem 11, 271–277 (2019).

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