Transition-Metal-Free Homopolymerization of Pyrrolo[2,3- d:5,4- d′]bisthiazoles via Nucleophilic Aromatic Substitution

Somnath Dey; Salahuddin Attar; Eric F. Manley; Salvador Moncho; Edward N. Brothers; Hassan S. Bazzi; Hugo Bronstein; Tobin J. Marks; Martin Heeney; Bob C. Schroeder; Mohammed Al-Hashimi

doi:10.1021/acsami.1c10858

Transition-Metal-Free Homopolymerization of Pyrrolo[2,3- d:5,4- d′]bisthiazoles via Nucleophilic Aromatic Substitution

Somnath Dey, Salahuddin Attar, Eric F. Manley, Salvador Moncho, Edward N. Brothers, Hassan S. Bazzi, Hugo Bronstein, Tobin J. Marks, Martin Heeney, Bob C. Schroeder^*, Mohammed Al-Hashimi^*

^*Corresponding author for this work

Chemistry

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

8 Scopus citations

Abstract

Novel methods to synthesize electron-deficient ?-conjugated polymers utilizing transition-metal-free coupling reactions for the use of nonfunctionalized monomers are attractive due to their improved atom economy and environmental prospective. Herein we describe the use of iPrMgCl·LiCl complex to afford thiazole-based conjugated polymers in the absence of any transition metal catalyst, that enables access to well-defined polymers with good molecular weights. The mechanistically distinct polymerizations proceeded via nucleophilic aromatic substitution (SNAr) reaction supported by density functional theory (DFT) calculations. This work demonstrates the first example of fully conjugated thiazole-based aromatic homopolymers without the need of any transition metal catalyst.

Original language	English (US)
Pages (from-to)	41094-41101
Number of pages	8
Journal	ACS Applied Materials and Interfaces
Volume	13
Issue number	34
DOIs	https://doi.org/10.1021/acsami.1c10858
State	Published - Sep 1 2021

Funding

This work was financially supported by the Qatar National Research Fund, project number: NPRP12S-0304-190227. B.C.S. acknowledges the UK Research and Innovation for Future Leaders Fellowship no. MR/S031952/1.

Keywords

conjugated polymer
nucleophilic aromatic substitution
organic semiconductor
thiazole
transition-metal-free

ASJC Scopus subject areas

General Materials Science

Access to Document

10.1021/acsami.1c10858

Cite this

Dey, S., Attar, S., Manley, E. F., Moncho, S., Brothers, E. N., Bazzi, H. S., Bronstein, H., Marks, T. J., Heeney, M., Schroeder, B. C., & Al-Hashimi, M. (2021). Transition-Metal-Free Homopolymerization of Pyrrolo[2,3- d:5,4- d′]bisthiazoles via Nucleophilic Aromatic Substitution. ACS Applied Materials and Interfaces, 13(34), 41094-41101. https://doi.org/10.1021/acsami.1c10858

@article{f2edf8a6ba5742bd80c9d50cbaaf2ad7,

title = "Transition-Metal-Free Homopolymerization of Pyrrolo[2,3- d:5,4- d′]bisthiazoles via Nucleophilic Aromatic Substitution",

abstract = "Novel methods to synthesize electron-deficient ?-conjugated polymers utilizing transition-metal-free coupling reactions for the use of nonfunctionalized monomers are attractive due to their improved atom economy and environmental prospective. Herein we describe the use of iPrMgCl·LiCl complex to afford thiazole-based conjugated polymers in the absence of any transition metal catalyst, that enables access to well-defined polymers with good molecular weights. The mechanistically distinct polymerizations proceeded via nucleophilic aromatic substitution (SNAr) reaction supported by density functional theory (DFT) calculations. This work demonstrates the first example of fully conjugated thiazole-based aromatic homopolymers without the need of any transition metal catalyst.",

keywords = "conjugated polymer, nucleophilic aromatic substitution, organic semiconductor, thiazole, transition-metal-free",

author = "Somnath Dey and Salahuddin Attar and Manley, {Eric F.} and Salvador Moncho and Brothers, {Edward N.} and Bazzi, {Hassan S.} and Hugo Bronstein and Marks, {Tobin J.} and Martin Heeney and Schroeder, {Bob C.} and Mohammed Al-Hashimi",

note = "Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = sep,

day = "1",

doi = "10.1021/acsami.1c10858",

language = "English (US)",

volume = "13",

pages = "41094--41101",

journal = "ACS Applied Materials and Interfaces",

issn = "1944-8244",

publisher = "American Chemical Society",

number = "34",

}

Dey, S, Attar, S, Manley, EF, Moncho, S, Brothers, EN, Bazzi, HS, Bronstein, H, Marks, TJ, Heeney, M, Schroeder, BC & Al-Hashimi, M 2021, 'Transition-Metal-Free Homopolymerization of Pyrrolo[2,3- d:5,4- d′]bisthiazoles via Nucleophilic Aromatic Substitution', ACS Applied Materials and Interfaces, vol. 13, no. 34, pp. 41094-41101. https://doi.org/10.1021/acsami.1c10858

TY - JOUR

T1 - Transition-Metal-Free Homopolymerization of Pyrrolo[2,3- d:5,4- d′]bisthiazoles via Nucleophilic Aromatic Substitution

AU - Dey, Somnath

AU - Attar, Salahuddin

AU - Manley, Eric F.

AU - Moncho, Salvador

AU - Brothers, Edward N.

AU - Bazzi, Hassan S.

AU - Bronstein, Hugo

AU - Marks, Tobin J.

AU - Heeney, Martin

AU - Schroeder, Bob C.

AU - Al-Hashimi, Mohammed

PY - 2021/9/1

Y1 - 2021/9/1

N2 - Novel methods to synthesize electron-deficient ?-conjugated polymers utilizing transition-metal-free coupling reactions for the use of nonfunctionalized monomers are attractive due to their improved atom economy and environmental prospective. Herein we describe the use of iPrMgCl·LiCl complex to afford thiazole-based conjugated polymers in the absence of any transition metal catalyst, that enables access to well-defined polymers with good molecular weights. The mechanistically distinct polymerizations proceeded via nucleophilic aromatic substitution (SNAr) reaction supported by density functional theory (DFT) calculations. This work demonstrates the first example of fully conjugated thiazole-based aromatic homopolymers without the need of any transition metal catalyst.

AB - Novel methods to synthesize electron-deficient ?-conjugated polymers utilizing transition-metal-free coupling reactions for the use of nonfunctionalized monomers are attractive due to their improved atom economy and environmental prospective. Herein we describe the use of iPrMgCl·LiCl complex to afford thiazole-based conjugated polymers in the absence of any transition metal catalyst, that enables access to well-defined polymers with good molecular weights. The mechanistically distinct polymerizations proceeded via nucleophilic aromatic substitution (SNAr) reaction supported by density functional theory (DFT) calculations. This work demonstrates the first example of fully conjugated thiazole-based aromatic homopolymers without the need of any transition metal catalyst.

KW - conjugated polymer

KW - nucleophilic aromatic substitution

KW - organic semiconductor

KW - thiazole

KW - transition-metal-free

UR - http://www.scopus.com/inward/record.url?scp=85114420339&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85114420339&partnerID=8YFLogxK

U2 - 10.1021/acsami.1c10858

DO - 10.1021/acsami.1c10858

M3 - Article

C2 - 34410686

AN - SCOPUS:85114420339

SN - 1944-8244

VL - 13

SP - 41094

EP - 41101

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

IS - 34

ER -

Transition-Metal-Free Homopolymerization of Pyrrolo[2,3- d:5,4- d′]bisthiazoles via Nucleophilic Aromatic Substitution

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this