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    Isolation of Living Conjugated Polymer Chains
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    • Shuyang Ye
      Shuyang Ye
      Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada
      More by Shuyang Ye
    • Susan Cheng
      Susan Cheng
      Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada
      More by Susan Cheng
    • Adam A. Pollit
      Adam A. Pollit
      Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada
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    • Matthew W. Forbes
      Matthew W. Forbes
      Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada
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    • Dwight S. Seferos*
      Dwight S. Seferos
      Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada
      Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario M5S 3E5, Canada
      *[email protected]
      More by Dwight S. Seferos
      Orcidhttp://orcid.org/0000-0001-8742-8058
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 25, 11244–11251
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    https://doi.org/10.1021/jacs.0c04379
    Published May 28, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Living polymerizations currently play a central role in polymer chemistry. However, one feature of these polymerizations is often overlooked, namely, the isolation of living polymer chains. Herein we report the isolation of living π-conjugated polymer chains, synthesized by catalyst-transfer polycondensation. Successful preservation of the nickel complex at polymer chain ends is evidenced by nuclear magnetic resonance spectroscopy, end group analysis, and chain extension experiments. When characterizing living chains by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, we discovered a unique photoionization–photodissociation fragmentation process for polymers containing a nickel phosphine end group. Living chains are isolated for several types of conjugated polymers as well as discrete living oligomers. Additionally, we are able to recycle the catalysts from the isolated polymer chains. Catalyst recycling after π-conjugated polymerization has previously been impossible without chain isolation. This strategy not only exhibits general applicability to different monomers but also has far-reaching potential for other catalytic systems.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c04379.

    • Instrumentation information, synthesis and characterization of nickel complexes, TGA measurements, and detailed NMR and MALDI-TOF-MS spectra (PDF)

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    Cited By

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    This article is cited by 22 publications.

    1. Jie Wang, Donglai Tian, Xuezheng Zhang, Huanghao Pan, Yun Ding, Guiyou Wang, Aiguo Hu. Synthesis of Narrowly Distributed α,ω-Bifunctionalized Conjugated Polymers. Macromolecules 2023, 56 (15) , 5835-5842. https://doi.org/10.1021/acs.macromol.3c00870
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    11. Chaoran Xu, Jin Dong, Congze He, Jie Yun, Xiangcheng Pan. Precise control of conjugated polymer synthesis from step-growth polymerization to iterative synthesis. Giant 2023, 14 , 100154. https://doi.org/10.1016/j.giant.2023.100154
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    13. Li Zhou, Lei Xu, Xue Song, Shu-Ming Kang, Na Liu, Zong-Quan Wu. Nickel(II)-catalyzed living polymerization of diazoacetates toward polycarbene homopolymer and polythiophene-block-polycarbene copolymers. Nature Communications 2022, 13 (1) https://doi.org/10.1038/s41467-022-28475-6
    14. Hao Xu, Shuyang Ye, Ruyan Zhao, Dwight S. Seferos. Homogeneous Synthesis of Monodisperse Sequence‐Defined Conjugated Oligomers by Temperature Cycling. Angewandte Chemie 2022, 134 (39) https://doi.org/10.1002/ange.202210340
    15. Hao Xu, Shuyang Ye, Ruyan Zhao, Dwight S. Seferos. Homogeneous Synthesis of Monodisperse Sequence‐Defined Conjugated Oligomers by Temperature Cycling. Angewandte Chemie International Edition 2022, 61 (39) https://doi.org/10.1002/anie.202210340
    16. Shuyang Ye, Victor Lotocki, Hao Xu, Dwight S. Seferos. Group 16 conjugated polymers based on furan, thiophene, selenophene, and tellurophene. Chemical Society Reviews 2022, 51 (15) , 6442-6474. https://doi.org/10.1039/D2CS00139J
    17. Anthony J. Varni, Manami Kawakami, Michael V. Bautista, Kevin J.T. Noonan. Polymerization Reactions via Cross Coupling. 2022, 465-510. https://doi.org/10.1016/B978-0-12-820206-7.00115-3
    18. Garion E. J. Hicks, Sheng Li, Nimrat K. Obhi, Charles N. Jarrett‐Wilkins, Dwight S. Seferos. Programmable Assembly of π‐Conjugated Polymers. Advanced Materials 2021, 33 (46) https://doi.org/10.1002/adma.202006287
    19. Vladimir Kardelis, Maria M. Denk, Alex Adronov. Click‐Functionalization of a Poly(Tetrazine‐co‐Fluorene)‐Conjugated Polymer with a Series of trans ‐Cyclooctene Derivatives. Angewandte Chemie 2021, 133 (6) , 3017-3023. https://doi.org/10.1002/ange.202010795
    20. Vladimir Kardelis, Maria M. Denk, Alex Adronov. Click‐Functionalization of a Poly(Tetrazine‐co‐Fluorene)‐Conjugated Polymer with a Series of trans ‐Cyclooctene Derivatives. Angewandte Chemie International Edition 2021, 60 (6) , 2980-2986. https://doi.org/10.1002/anie.202010795
    21. Tomohiro Kubo, Morgan S. Young, Kendra D. Souther, Matthew D. Hannigan, Anne J. McNeil. Air‐tolerant poly(3‐hexylthiophene) synthesis via catalyst‐transfer polymerization. Journal of Polymer Science 2021, 59 (3) , 268-273. https://doi.org/10.1002/pol.20200788
    22. Adam A. Pollit, Alan J. Lough, Dwight S. Seferos. Examining the Spin State and Redox Chemistry of Ni(Diimine) Catalysts during the Synthesis of π‐Conjugated Polymers. Macromolecular Chemistry and Physics 2020, 221 (24) https://doi.org/10.1002/macp.202000321
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 25, 11244–11251
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.0c04379
    Published May 28, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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