Benzodithiophene homopolymers via direct (hetero)arylation polymerization

Calvin L. Cicha; Samuel N. Gockel; Andrew J. Helmin; Wyatt D. Wilcox; Daron E. Janzen; Ted M. Pappenfus

doi:10.1007/s00289-018-2346-6

Benzodithiophene homopolymers via direct (hetero)arylation polymerization

Calvin L. Cicha, Samuel N. Gockel, Andrew J. Helmin, Wyatt D. Wilcox, Daron E. Janzen, Ted M. Pappenfus

Chemistry (Morris)

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

Direct (hetero)arylation polymerization (DHAP) of a monobrominated benzo[1,2-b:4,5-b′]dithiophene monomer using the Herrmann–Beller catalyst with a tertiary phosphine provided benzodithiophene homopolymers in good yields. Employing both P(o-OMePh)₃ and P(o-NMe₂Ph)₃ as the phosphine ligands gave well-defined polymers—with the later phosphine providing a higher molecular weight polymer. The preparation of a benzodithiophene (BDT) trimer was used to assist in the assignment of the ¹H NMR spectra of the synthesized polymers which show largely defect-free couplings. The optical spectra of polymers formed via DHAP and those prepared using traditional Stille couplings are essentially identical, which further confirms the presence of well-defined BDT–BDT couplings along the conjugated polymer chain. These results confirm that carboxylic acid additives are not always necessary to suppress defects in DHAP polymerizations and that DHAP is a viable alternative to traditional Stille coupling for the preparation of benzodithiophene homopolymers.

Original language	English (US)
Pages (from-to)	5667-5675
Number of pages	9
Journal	Polymer Bulletin
Volume	75
Issue number	12
DOIs	https://doi.org/10.1007/s00289-018-2346-6
State	Published - Dec 1 2018

Bibliographical note

Funding Information:
acknowledge the Howard Hughes Medical Institute (HHMI) Pathways to Science Program for financial assistance.

Funding Information:
Acknowledgements T.M.P. acknowledges the following: (1) University of Minnesota, Morris (UMM) Faculty Research Enhancement Funds supported by the University of Minnesota Office of the Vice President for Research and the UMM Division of Science and Mathematics for financial assistance, (2) The Supercomputing Institute of the University of Minnesota, (3) Seth C. Rasmussen for helpful suggestions and insight, and (4) Diane Hopkins Whelan for administrative support. T.M.P., A.J.H. and W.D.W.

Publisher Copyright:
© 2018, Springer-Verlag GmbH Germany, part of Springer Nature.

Keywords

Benzodithiophene
Conjugated polymers
Direct arylation polymerization

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10.1007/s00289-018-2346-6

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title = "Benzodithiophene homopolymers via direct (hetero)arylation polymerization",

abstract = "Direct (hetero)arylation polymerization (DHAP) of a monobrominated benzo[1,2-b:4,5-b′]dithiophene monomer using the Herrmann–Beller catalyst with a tertiary phosphine provided benzodithiophene homopolymers in good yields. Employing both P(o-OMePh)3 and P(o-NMe2Ph)3 as the phosphine ligands gave well-defined polymers—with the later phosphine providing a higher molecular weight polymer. The preparation of a benzodithiophene (BDT) trimer was used to assist in the assignment of the 1H NMR spectra of the synthesized polymers which show largely defect-free couplings. The optical spectra of polymers formed via DHAP and those prepared using traditional Stille couplings are essentially identical, which further confirms the presence of well-defined BDT–BDT couplings along the conjugated polymer chain. These results confirm that carboxylic acid additives are not always necessary to suppress defects in DHAP polymerizations and that DHAP is a viable alternative to traditional Stille coupling for the preparation of benzodithiophene homopolymers.",

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note = "Funding Information: acknowledge the Howard Hughes Medical Institute (HHMI) Pathways to Science Program for financial assistance. Funding Information: Acknowledgements T.M.P. acknowledges the following: (1) University of Minnesota, Morris (UMM) Faculty Research Enhancement Funds supported by the University of Minnesota Office of the Vice President for Research and the UMM Division of Science and Mathematics for financial assistance, (2) The Supercomputing Institute of the University of Minnesota, (3) Seth C. Rasmussen for helpful suggestions and insight, and (4) Diane Hopkins Whelan for administrative support. T.M.P., A.J.H. and W.D.W. Publisher Copyright: {\textcopyright} 2018, Springer-Verlag GmbH Germany, part of Springer Nature.",

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AU - Pappenfus, Ted M.

N1 - Funding Information: acknowledge the Howard Hughes Medical Institute (HHMI) Pathways to Science Program for financial assistance. Funding Information: Acknowledgements T.M.P. acknowledges the following: (1) University of Minnesota, Morris (UMM) Faculty Research Enhancement Funds supported by the University of Minnesota Office of the Vice President for Research and the UMM Division of Science and Mathematics for financial assistance, (2) The Supercomputing Institute of the University of Minnesota, (3) Seth C. Rasmussen for helpful suggestions and insight, and (4) Diane Hopkins Whelan for administrative support. T.M.P., A.J.H. and W.D.W. Publisher Copyright: © 2018, Springer-Verlag GmbH Germany, part of Springer Nature.

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N2 - Direct (hetero)arylation polymerization (DHAP) of a monobrominated benzo[1,2-b:4,5-b′]dithiophene monomer using the Herrmann–Beller catalyst with a tertiary phosphine provided benzodithiophene homopolymers in good yields. Employing both P(o-OMePh)3 and P(o-NMe2Ph)3 as the phosphine ligands gave well-defined polymers—with the later phosphine providing a higher molecular weight polymer. The preparation of a benzodithiophene (BDT) trimer was used to assist in the assignment of the 1H NMR spectra of the synthesized polymers which show largely defect-free couplings. The optical spectra of polymers formed via DHAP and those prepared using traditional Stille couplings are essentially identical, which further confirms the presence of well-defined BDT–BDT couplings along the conjugated polymer chain. These results confirm that carboxylic acid additives are not always necessary to suppress defects in DHAP polymerizations and that DHAP is a viable alternative to traditional Stille coupling for the preparation of benzodithiophene homopolymers.

AB - Direct (hetero)arylation polymerization (DHAP) of a monobrominated benzo[1,2-b:4,5-b′]dithiophene monomer using the Herrmann–Beller catalyst with a tertiary phosphine provided benzodithiophene homopolymers in good yields. Employing both P(o-OMePh)3 and P(o-NMe2Ph)3 as the phosphine ligands gave well-defined polymers—with the later phosphine providing a higher molecular weight polymer. The preparation of a benzodithiophene (BDT) trimer was used to assist in the assignment of the 1H NMR spectra of the synthesized polymers which show largely defect-free couplings. The optical spectra of polymers formed via DHAP and those prepared using traditional Stille couplings are essentially identical, which further confirms the presence of well-defined BDT–BDT couplings along the conjugated polymer chain. These results confirm that carboxylic acid additives are not always necessary to suppress defects in DHAP polymerizations and that DHAP is a viable alternative to traditional Stille coupling for the preparation of benzodithiophene homopolymers.

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Benzodithiophene homopolymers via direct (hetero)arylation polymerization

Abstract

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