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

ABSTRACT 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 (_M__n_) 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

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BEING VIEWED BY OTHERS GENERAL ROOM-TEMPERATURE SUZUKI–MIYAURA POLYMERIZATION FOR ORGANIC ELECTRONICS Article 29 January 2024 CONJUGATED POLYMERS BASED ON SELENOPHENE BUILDING BLOCKS Article

Open access 06 December 2022 EFFICIENT ROOM TEMPERATURE CATALYTIC SYNTHESIS OF ALTERNATING CONJUGATED COPOLYMERS VIA C-S BOND ACTIVATION Article Open access 10 January 2022 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

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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. AUTHOR INFORMATION Author notes

* The authors contributed equally: Zhenjie Ni, Hanlin Wang and Huanli Dong. AUTHORS AND AFFILIATIONS * 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 Yanfeng Dang, Xiaotao Zhang & Wenping Hu * Collaborative Innovation Center of Chemical Science and Engineering, Tianjin,

China Wenping Hu Authors * Zhenjie Ni View author publications You can also search for this author inPubMed Google Scholar * Hanlin Wang View author publications You can also search for this

author inPubMed Google Scholar * Huanli Dong View author publications You can also search for this author inPubMed Google Scholar * Yanfeng Dang View author publications You can also search

for this author inPubMed Google Scholar * Qiang Zhao View author publications You can also search for this author inPubMed Google Scholar * Xiaotao Zhang View author publications You can

also search for this author inPubMed Google Scholar * Wenping Hu View author publications You can also search for this author inPubMed Google Scholar CONTRIBUTIONS 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. CORRESPONDING AUTHOR Correspondence to Wenping Hu. ETHICS

DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. ADDITIONAL INFORMATION PUBLISHER’S NOTE: Springer Nature remains neutral with regard to jurisdictional claims in

published maps and institutional affiliations. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Synthetic procedures; Characterization, including NMR spectra and GPC traces;

Computational details RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE 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). https://doi.org/10.1038/s41557-018-0200-y Download citation * Received:

22 May 2018 * Accepted: 30 November 2018 * Published: 28 January 2019 * Issue Date: March 2019 * DOI: https://doi.org/10.1038/s41557-018-0200-y SHARE THIS ARTICLE Anyone you share the

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