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Intramolecular catalyst transfer on silylene group between benzene rings in Suzuki–Miyaura coupling reaction: synthesis of σ−π conjugated cyclic polymers

Polymer Journal (2024)Cite this article

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Suzuki–Miyaura polycondensation, employing non-toxic boronic acid (ester), aryl halide, and a Pd catalyst in solvent containing water, is a very powerful polymerization methods for polyarylenes [1,2,3]. Herein, a unique Suzuki–Miyaura polycondensation methodology is developed based on intramolecular catalyst transfer on aromatic rings. The polymerization of haloareneboronic acid (ester) as an AB monomer proceeds in a chain-growth polymerization manner, affording well-defined π-conjugated polymers [4]. The polymerization of dibromoarylene and arylenediboronic acid (ester) monomers affords high-molecular-weight polymers and cyclic polymers, depending on the position of the reaction sites of the arylenes (if at least one of the two monomers has a kinked structure, a cyclic polymer is selectively formed), even when excess dibromoarylene is used [5]. Furthermore, Pd catalyst transfer can occur even when a functional group, such as a methylene, carbonyl, sulfonyl, or amino group or an ether linkage, is present between the benzene rings of bis(bromophenylene) in the polycondensation with arylenediboronic acid [6].

We first examined the Suzuki–Miyaura coupling reaction of 2 equivalents of p-bis(bromophenylene) 1, which contained a silylene group, with 1.0 equivalent of m-isobutoxyphenylboronic acid (3) in the presence of 5 mol% of tBu3PPd precatalyst 4 and CsF/18-crown-6 as a base in THF/water at ambient temperature to see whether the Pd catalyst would transfer on the silylene group (Fig. 1). If the catalyst transfers on the benzene rings and the silylene group in 1 after the first substitution with 3, the disubstituted product (DP) should be selectively obtained rather than the monosubstituted product (MP). The DP/MP ratio was determined from the 1H NMR spectra of the crude products on the basis of the spectra of DP and MP isolated in other experiments (Figs. S1, S2). We found that only DP was obtained, irrespective of the substituents on the silylene group (Table 1). This result demonstrates that the Pd catalyst undergoes intramolecular catalyst transfer on the silylene group between the benzene rings.

Table 1 Proportions of DP/MP in the Suzuki–Miyaura coupling reaction of 1 with 3 in the presence of 4a
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References

  1. Sakamoto J, Rehahn M, Wegner G, Schlüter AD. Suzuki polycondensation: polyarylenes à la carte. Macromol Rapid Commun. 2009;30:653–87.

    Article  CAS  PubMed  Google Scholar 

  2. Sakamoto J, Rehahn M, Schlüter D. Suzuki polycondensation: a powerful tool for polyarylene synthesis. Design and synthesis of conjugated polymers; 2010. p. 45–90.

  3. Krishna A, Lunchev AV, Grimsdale AC. Suzuki polycondensation. Synthetic methods for conjugated polymers and carbon materials; 2017. p. 59–95.

  4. Yokozawa T, Ohta Y. Chapter 1 Controlled synthesis of conjugated polymers in catalyst-transfer condensation polymerization: Monomers and catalysts. Semiconducting polymers: controlled synthesis and microstructure: The Royal Society of Chemistry; 2017. p. 1–37.

  5. Yokozawa T, Ohta Y. Nonstoichiometric Suzuki–Miyaura polycondensation for the synthesis of aromatic polymers. Polym Sci Ser C. 2020;62:78–89.

    Article  Google Scholar 

  6. Yokozawa T, Harada N, Sugita H, Ohta Y. Intramolecular catalyst transfer on a variety of functional groups between benzene rings in a Suzuki–Miyaura coupling reaction. Chem Eur J. 2019;25:10059–62.

    Article  CAS  PubMed  Google Scholar 

  7. Fang M-C, Watanabe A, Matsuda M. Emission spectra of σ−π-conjugated organosilicon copolymers consisting of alternating dimethylsilylene and aromatic units. Macromolecules. 1996;29:6807–13.

    Article  CAS  Google Scholar 

  8. van Walree CA, Roest MR, Schuddeboom W, Jenneskens LW, Verhoeven JW, Warman JM, et al. Comparison between sime2 and cme2 spacers as σ-bridges for photoinduced charge transfer. J Am Chem Soc. 1996;118:8395–407.

    Article  Google Scholar 

  9. Chang Y-T, Sharma S, Hung M-K, Lee Y-H, Chen S-A. Bipolar and unipolar silylene-diphenylene σ-π conjugated polymer route for highly efficient electrophosphorescence. Sci Rep. 2016;6:38404.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  10. Hung M-K, Tsai K-W, Sharma S, Lei J, Wu J-Y, Chen S-A. Optoelectronic properties of high triplet σ–π-conjugated poly[(biphenyl group iv-a atom (C, Si, Ge, Sn)] backbones. ACS Appl Mater. 2019;11:36895–904.

    Article  CAS  Google Scholar 

  11. Li X, Bai Q, Li J, Lu F, Sun X, Lu P. Synthesis and properties of wide bandgap polymers based on tetraphenylsilane and their applications as hosts in electrophosphorescent devices. N J Chem. 2018;42:3344–9.

    Article  CAS  Google Scholar 

  12. Yeh H-C, Chien C-H, Shih P-I, Yuan M-C, Shu C-F. Polymers derived from 3,6-fluorene and tetraphenylsilane derivatives: Solution-processable host materials for green phosphorescent oleds. Macromolecules. 2008;41:3801–7.

    Article  CAS  Google Scholar 

  13. Kim GW, Yang DR, Kim YC, Yang HI, Fan JG, Lee C-H, et al. Di(biphenyl)silane and carbazole based bipolar host materials for highly efficient blue phosphorescent oleds. Dyes Pigm. 2017;136:8–16.

    Article  CAS  Google Scholar 

  14. Sobarzo PA, Mariman AP, Sánchez CO, Hauyon RA, Rodríguez-González FE, Medina J, et al. Comparison between poly(azomethine)s and poly(p-phenylvinylene)s containing a di-r-diphenylsilane (r = methyl or phenyl) moiety. Optical, electronic and thermal properties. Eur Polym J. 2021;159:110714.

    Article  CAS  Google Scholar 

  15. Sobarzo PA, Jessop IA, Mariman AP, González AF, Saldías C, Schott E, et al. New thiophene-based poly(azomethine)s bearing tetraphenylsilane moieties along their backbone. Optical, electronic, thermal properties and theoretical calculations. Eur Polym J. 2020;130:109658.

    Article  CAS  Google Scholar 

  16. Tundidor-Camba A, González-Henríquez CM, Sarabia-Vallejos MA, Tagle LH, Sobarzo PA, González A, et al. Diphenylsilane-containing linear and rigid whole aromatic poly(azomethine)s. Structural and physical characterization. Polymer. 2018;150:232–43.

    Article  CAS  Google Scholar 

  17. Sobarzo PA, González AF, Schott E, Tagle LH, Tundidor-Camba A, González-Henríquez C, et al. New triphenylamine-based oligomeric schiff bases containing tetraphenylsilane moieties in the backbone. Polymers. 2019;11:216.

    Article  PubMed  PubMed Central  Google Scholar 

  18. Ohshita J, Watanabe T, Kanaya D, Ohsaki H, Ishikawa M, Ago H, et al. Polymeric organosilicon systems. 22. Synthesis and photochemical properties of poly[(disilanylene)oligophenylylenes] and poly[(silylene)biphenylylenes]. Organometallics. 1994;13:5002–12.

    Article  CAS  Google Scholar 

  19. Sugita H, Nojima M, Ohta Y, Yokozawa T. Unusual cyclic polymerization through Suzuki–Miyaura coupling of polyphenylene bearing diboronate at both ends with excess dibromophenylene. Chem Commun. 2017;53:396–9.

    Article  CAS  Google Scholar 

  20. Karatsu T. Photochemistry and photophysics of organomonosilane and oligosilanes: updating their studies on conformation and intramolecular interactions. J Photochem Photobio C: Photochem Rev. 2008;9:111–37.

    Article  CAS  Google Scholar 

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Acknowledgements

This study was supported by the MEXT-Supported Program for the Strategic Research Foundation at Private Universities (No. S1311032), 2013-2018, and by a Grant in Aid (No. 15H03819) for Scientific Research from the Japan Society for the Promotion of Science (JSPS).

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  1. Department of Materials and Life Chemistry, Faculty of Engineering, Kanagawa University, Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686, Japan

    Natsumi Harada, Rina Yachida, Ryusuke Shimada, Yoshihiro Ohta & Tsutomu Yokozawa

  2. Department of Applied Chemistry, Faculty of Chemistry and Biochemistry, Kanagawa University, Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686, Japan

    Takayoshi Katoh, Sena Hashimoto, Yoshihiro Ohta, Izumi Iwakura & Tsutomu Yokozawa

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Harada, N., Yachida, R., Shimada, R. et al. Intramolecular catalyst transfer on silylene group between benzene rings in Suzuki–Miyaura coupling reaction: synthesis of σ−π conjugated cyclic polymers. Polym J (2024). https://doi.org/10.1038/s41428-024-00913-w

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