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Suzuki–Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers

Herein, we report the Suzuki–Miyaura catalyst-transfer polycondensation (SCTP) of triolborate-type carbazole monomers, i.e., potassium 3-(6-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl)triolborate (M1) and potassium 2-(7-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl) triolborate (M2), as an efficient and...

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Autores principales: Kobayashi, Saburo, Ashiya, Mayoh, Yamamoto, Takuya, Tajima, Kenji, Yamamoto, Yasunori, Isono, Takuya, Satoh, Toshifumi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8659485/
https://www.ncbi.nlm.nih.gov/pubmed/34883672
http://dx.doi.org/10.3390/polym13234168
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author Kobayashi, Saburo
Ashiya, Mayoh
Yamamoto, Takuya
Tajima, Kenji
Yamamoto, Yasunori
Isono, Takuya
Satoh, Toshifumi
author_facet Kobayashi, Saburo
Ashiya, Mayoh
Yamamoto, Takuya
Tajima, Kenji
Yamamoto, Yasunori
Isono, Takuya
Satoh, Toshifumi
author_sort Kobayashi, Saburo
collection PubMed
description Herein, we report the Suzuki–Miyaura catalyst-transfer polycondensation (SCTP) of triolborate-type carbazole monomers, i.e., potassium 3-(6-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl)triolborate (M1) and potassium 2-(7-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl) triolborate (M2), as an efficient and versatile approach for precisely synthesizing poly[9-(2-octyldodecyl)-3,6-carbazole] (3,6-PCz) and poly[9-(2-octyldodecyl)-2,7-carbazole] (2,7-PCz), respectively. The SCTP of triolborate-type carbazole monomers was performed in a mixture of THF/H(2)O using an initiating system consisted of 4-iodobenzyl alcohol, Pd(2)(dba)(3)•CHCl(3), and t-Bu(3)P. In the SCTP of M1, cyclic by-product formation was confirmed, as reported for the corresponding pinacolboronate-type monomer. By optimizing the reaction temperature and reaction time, we successfully synthesized linear end-functionalized 3,6-PCz for the first time. The SCTP of M2 proceeded with almost no side reaction, yielding 2,7-PCz with a functional initiator residue at the α-chain end. Kinetic and block copolymerization experiments demonstrated that the SCTP of M2 proceeded in a chain-growth and controlled/living polymerization manner. This is a novel study on the synthesis of 2,7-PCz via SCTP. By taking advantage of the well-controlled nature of this polymerization system, we demonstrated the synthesis of high-molecular-weight 2,7-PCzs (M(n) = 5–38 kg mol(−1)) with a relatively narrow Ð(M) (1.35–1.48). Furthermore, we successfully synthesized fluorene/carbazole copolymers as well as 2,7-PCz-containing diblock copolymers, demonstrating the versatility of the present polymerization system as a novel synthetic strategy for well-defined polycarbazole-based materials.
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spelling pubmed-86594852021-12-10 Suzuki–Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers Kobayashi, Saburo Ashiya, Mayoh Yamamoto, Takuya Tajima, Kenji Yamamoto, Yasunori Isono, Takuya Satoh, Toshifumi Polymers (Basel) Article Herein, we report the Suzuki–Miyaura catalyst-transfer polycondensation (SCTP) of triolborate-type carbazole monomers, i.e., potassium 3-(6-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl)triolborate (M1) and potassium 2-(7-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl) triolborate (M2), as an efficient and versatile approach for precisely synthesizing poly[9-(2-octyldodecyl)-3,6-carbazole] (3,6-PCz) and poly[9-(2-octyldodecyl)-2,7-carbazole] (2,7-PCz), respectively. The SCTP of triolborate-type carbazole monomers was performed in a mixture of THF/H(2)O using an initiating system consisted of 4-iodobenzyl alcohol, Pd(2)(dba)(3)•CHCl(3), and t-Bu(3)P. In the SCTP of M1, cyclic by-product formation was confirmed, as reported for the corresponding pinacolboronate-type monomer. By optimizing the reaction temperature and reaction time, we successfully synthesized linear end-functionalized 3,6-PCz for the first time. The SCTP of M2 proceeded with almost no side reaction, yielding 2,7-PCz with a functional initiator residue at the α-chain end. Kinetic and block copolymerization experiments demonstrated that the SCTP of M2 proceeded in a chain-growth and controlled/living polymerization manner. This is a novel study on the synthesis of 2,7-PCz via SCTP. By taking advantage of the well-controlled nature of this polymerization system, we demonstrated the synthesis of high-molecular-weight 2,7-PCzs (M(n) = 5–38 kg mol(−1)) with a relatively narrow Ð(M) (1.35–1.48). Furthermore, we successfully synthesized fluorene/carbazole copolymers as well as 2,7-PCz-containing diblock copolymers, demonstrating the versatility of the present polymerization system as a novel synthetic strategy for well-defined polycarbazole-based materials. MDPI 2021-11-28 /pmc/articles/PMC8659485/ /pubmed/34883672 http://dx.doi.org/10.3390/polym13234168 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Kobayashi, Saburo
Ashiya, Mayoh
Yamamoto, Takuya
Tajima, Kenji
Yamamoto, Yasunori
Isono, Takuya
Satoh, Toshifumi
Suzuki–Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers
title Suzuki–Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers
title_full Suzuki–Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers
title_fullStr Suzuki–Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers
title_full_unstemmed Suzuki–Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers
title_short Suzuki–Miyaura Catalyst-Transfer Polycondensation of Triolborate-Type Carbazole Monomers
title_sort suzuki–miyaura catalyst-transfer polycondensation of triolborate-type carbazole monomers
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8659485/
https://www.ncbi.nlm.nih.gov/pubmed/34883672
http://dx.doi.org/10.3390/polym13234168
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