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Regiocontrolled synthesis of ester-functionalized polythiophenes via direct arylation polycondensation

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Abstract

A series of ester-functionalized polythiophenes (P3OETs) with precisely controlled head-to-tail (HT) ratios was synthesized via palladium-catalyzed direct arylation polycondensation (DArP). The ionization potentials and optical bandgaps of P3OETs decreased as their HT ratios increased because of the increased backbone coplanarity and extensive π-electron delocalization. The method of precisely controlling the regioregularity and HT ratio can contribute to the design of new polythiophene derivatives with enhanced electronic functionality.

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References

  1. McCullough RD. The chemistry of conducting polythiophenes. Adv Mater. 1998;10:93–116.

    Article  CAS  Google Scholar 

  2. Günes S, Neugebauer H, Sariciftci NS. Conjugated polymer-based organic solar cells. Chem Rev. 2007;107:13241338.

    Article  Google Scholar 

  3. Sirringhaus H, Brown PJ, Friend RH, Nielsen MM, Bechgaard K, Langeveld-Voss BMW, et al. Two-dimensional charge transport in self-organized, high-mobility conjugated polymers. Nature. 1999;401:685–8.

    Article  CAS  Google Scholar 

  4. Mori T, Komiyama H, Ichikawa T, Yasuda T. A liquid-crystalline semiconducting polymer based on thienylenevvinylene–thienylene: enhanced hole mobilities by mesomorphic molecular ordering and thermoplastic shape-deformable characteristics. Polym J. 2020;52:313–21.

    Article  CAS  Google Scholar 

  5. Zhang M, Guo X, Ma W, Ade H, Hou J. A polythiophene derivative with superior properties for practical application in polymer solar cells. Adv Mater. 2014;26:5880–5.

    Article  CAS  Google Scholar 

  6. Qin Y, Uddin MA, Chen Y, Jang B, Zhao K, Zheng Z, et al. Highly efficient fullerene-free polymer solar cells fabricated with polythiophene derivatives. Adv Mater. 2016;28:9416–22.

    Article  CAS  Google Scholar 

  7. Heuvel R, Colberts FJM, Wienk MM, Janssen RAJ. Thermal behaviour of dicarboxylic ester bithiophene polymers exhibiting a high open-circuit voltage. J Mater Chem C. 2018;6:3731–42.

    Article  CAS  Google Scholar 

  8. Wang Q, Li M, Zhang X, Qin Y, Wang J, Zhang J, et al. Carboxylate-substituted polythiophenes for efficient fullerene-free polymer solar cells: The effect of chlorination on their properties. Macromolecules. 2019;52:4464–74.

    Article  CAS  Google Scholar 

  9. Li S, Ye L, Zhao W, Yan H, Yang B, Liu D, et al. A wide band gap polymer with a deep highest occupied molecular orbital level enables 14.2% efficiency in polymer solar cells. J Am Chem Soc. 2018;140:7159–67.

    Article  CAS  Google Scholar 

  10. Pomerantz M, Yang H, Cheng Y. Poly(alkyl thiophene-3-carboxylates). Synthesis and characterization of polythiophenes with a carbonyl group directly attached to the ring. Macromolecules. 1995;28:5706–8.

    Article  CAS  Google Scholar 

  11. Pomerantz M, Cheng Y, Kasim RK, Elsenbaumer RL. Poly(alkyl thiophene-3-carboxylates). Synthesis, properties and electroluminescence studies of polythiophenes containing a carbonyl group directly attached to the ring. J Mater Chem. 1999;9:2155–63.

    Article  CAS  Google Scholar 

  12. Qiu Y, Worch JC, Fortney A, Gayathri C, Gil RR, Noonan KJT. Nickel-catalyzed Suzuki polycondensation for controlled synthesis of ester-functionalized conjugated polymers. Macromolecules. 2016;49:4757–62.

    Article  CAS  Google Scholar 

  13. Gobalasingham NS, Noh S, Thompson BC. Palladium-catalyzed oxidative direct arylation polymerization (Oxi-DArP) of an ester-functionalized thiophene. Polym Chem. 2016;7:1623–31.

    Article  CAS  Google Scholar 

  14. Deng L, Zhang Q, Zhao L, Lu Y. Direct C-H coupling polymerization of asymmetric monomer: synthesis and properties of regioregular poly(alkyl thiophene-3-carboxylates). Eur Polym J. 2018;109:7281.

    Article  Google Scholar 

  15. Pankow RM, Ye L, Thompson BC. Influence of the ester directing group on the inhibition of defect formation in polythiophenes with direct arylation polymerization (DArP). Macromolecules. 2020;53:3315–24.

    Article  CAS  Google Scholar 

  16. P J-R, Grenier F, Blaskovits JT, Beaupré S, Leclerc M. Direct (hetero)arylation polymerization: simplicity for conjugated polymer synthesis. Chem Rev. 2016;116:14225–74.

    Article  Google Scholar 

  17. Nakabayashi K. Direct arylation polycondensation as conjugated polymer synthesis methodology. Polym J. 2018;50:475–83.

    Article  CAS  Google Scholar 

  18. Kuwabara J. Direct arylation polycondensation for synthesis of optoelectronic materials. Polym J. 2018;50:1099–106.

    Article  CAS  Google Scholar 

  19. Kuwabara J, Kanbara T. Facile synthesis of π-conjugated polymers via direct arylation polycondensation. Bull Chem Soc Jpn. 2019;92:152–61.

    Article  CAS  Google Scholar 

  20. Wkioka M, Ozawa F. Highly efficient catalysts for direct arylation polymerization (DArP). Asian J Org Chem. 2018;7:1206–16.

    Article  Google Scholar 

  21. Wang Q, Takita R, Kikuzaki Y, Ozawa F. Palladium-catalyzed dehydrohalogenative polycondensation of 2-bromo-3-hexylthiophene: an efficient approach to head-to-tail poly(3-hexylthiophene). J Am Chem Soc. 2010;132:11420–1.

    Article  CAS  Google Scholar 

  22. Lafrance M, Fagnou K. Pallladium-catalyzed benzene arylation: Incorporation of catalytic pivalic acid as a proton shuttle and a key element in catalyst design. J Am Chem Soc. 2006;128:16496–7.

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported in part by Grants-in-Aid for JSPS KAKENHI (Grant Nos. JP18H02048 (TY) and JP18J22297 (TM)), the Amano Institute of Technology (TY) and the Iwatani Naoji Foundation (TY). The authors acknowledge the support of the Cooperative Research Program “Network Joint Research Center for Materials and Devices”.

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Authors and Affiliations

  1. INAMORI Frontier Research Center (IFRC), Kyushu University, Fukuoka, Japan

    Taiki Menda, Tatsuya Mori & Takuma Yasuda

  2. Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, Fukuoka, Japan

    Taiki Menda, Tatsuya Mori & Takuma Yasuda

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  1. Taiki Menda
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  2. Tatsuya Mori
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  3. Takuma Yasuda
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Correspondence to Takuma Yasuda.

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Menda, T., Mori, T. & Yasuda, T. Regiocontrolled synthesis of ester-functionalized polythiophenes via direct arylation polycondensation. Polym J 53, 403–408 (2021). https://doi.org/10.1038/s41428-020-00421-7

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