Dialkoxybithiazole

A new building block for head-to-head polymer semiconductors

Xugang Guo, Jordan Quinn, Zhihua Chen, Hakan Usta, Yan Zheng, Yu Xia, Jonathan W. Hennek, Rocío Ponce Ortiz, Tobin J Marks, Antonio Facchetti

Research output: Contribution to journalArticle

115 Citations (Scopus)

Abstract

Polymer semiconductors have received great attention for organic electronics due to the low fabrication cost offered by solution-based printing techniques. To enable the desired solubility/processability and carrier mobility, polymers are functionalized with hydrocarbon chains by strategically manipulating the alkylation patterns. Note that head-to-head (HH) linkages have traditionally been avoided because the induced backbone torsion leads to poor π-π overlap and amorphous film microstructures, and hence to low carrier mobilities. We report here the synthesis of a new building block for HH linkages, 4,4′-dialkoxy-5,5′-bithiazole (BTzOR), and its incorporation into polymers for high performance organic thin-film transistors. The small oxygen van der Waals radius and intramolecular S(thiazolyl) ⋯O(alkoxy) attraction promote HH macromolecular architectures with extensive π-conjugation, low bandgaps (1.40-1.63 eV), and high crystallinity. In comparison to previously reported 3,3′-dialkoxy-2,2′-bithiophene (BTOR), BTzOR is a promising building block in view of thiazole geometric and electronic properties: (a) replacing (thiophene)C-H with (thiazole)N reduces steric encumbrance in -BTzOR-Ar.06-0.25 cm2/(V s)) in organic thin-film transistors, as well as enhanced Ion:Ioff ratios and greater ambient stability than the BTOR analogues. These geometric and electronic properties make BTzOR a promising building block for new classes of polymer semiconductors, and the synthetic route to BTzOR reported here should be adaptable to many other bithiazole-based building blocks.

Original languageEnglish
Pages (from-to)1986-1996
Number of pages11
JournalJournal of the American Chemical Society
Volume135
Issue number5
DOIs
Publication statusPublished - Feb 6 2013

Fingerprint

Semiconductors
Polymers
Semiconductor materials
Thiazoles
Carrier mobility
Thin film transistors
Electronic properties
Thiophenes
Printing
Alkylation
Thiophene
Amorphous films
Hydrocarbons
Torsional stress
Solubility
Energy gap
Electronic equipment
Ions
Oxygen
Costs and Cost Analysis

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Guo, X., Quinn, J., Chen, Z., Usta, H., Zheng, Y., Xia, Y., ... Facchetti, A. (2013). Dialkoxybithiazole: A new building block for head-to-head polymer semiconductors. Journal of the American Chemical Society, 135(5), 1986-1996. https://doi.org/10.1021/ja3120532

Dialkoxybithiazole : A new building block for head-to-head polymer semiconductors. / Guo, Xugang; Quinn, Jordan; Chen, Zhihua; Usta, Hakan; Zheng, Yan; Xia, Yu; Hennek, Jonathan W.; Ortiz, Rocío Ponce; Marks, Tobin J; Facchetti, Antonio.

In: Journal of the American Chemical Society, Vol. 135, No. 5, 06.02.2013, p. 1986-1996.

Research output: Contribution to journalArticle

Guo, X, Quinn, J, Chen, Z, Usta, H, Zheng, Y, Xia, Y, Hennek, JW, Ortiz, RP, Marks, TJ & Facchetti, A 2013, 'Dialkoxybithiazole: A new building block for head-to-head polymer semiconductors', Journal of the American Chemical Society, vol. 135, no. 5, pp. 1986-1996. https://doi.org/10.1021/ja3120532
Guo, Xugang ; Quinn, Jordan ; Chen, Zhihua ; Usta, Hakan ; Zheng, Yan ; Xia, Yu ; Hennek, Jonathan W. ; Ortiz, Rocío Ponce ; Marks, Tobin J ; Facchetti, Antonio. / Dialkoxybithiazole : A new building block for head-to-head polymer semiconductors. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 5. pp. 1986-1996.
@article{2b79e04b72ef458d826b33000a4f9cc8,
title = "Dialkoxybithiazole: A new building block for head-to-head polymer semiconductors",
abstract = "Polymer semiconductors have received great attention for organic electronics due to the low fabrication cost offered by solution-based printing techniques. To enable the desired solubility/processability and carrier mobility, polymers are functionalized with hydrocarbon chains by strategically manipulating the alkylation patterns. Note that head-to-head (HH) linkages have traditionally been avoided because the induced backbone torsion leads to poor π-π overlap and amorphous film microstructures, and hence to low carrier mobilities. We report here the synthesis of a new building block for HH linkages, 4,4′-dialkoxy-5,5′-bithiazole (BTzOR), and its incorporation into polymers for high performance organic thin-film transistors. The small oxygen van der Waals radius and intramolecular S(thiazolyl) ⋯O(alkoxy) attraction promote HH macromolecular architectures with extensive π-conjugation, low bandgaps (1.40-1.63 eV), and high crystallinity. In comparison to previously reported 3,3′-dialkoxy-2,2′-bithiophene (BTOR), BTzOR is a promising building block in view of thiazole geometric and electronic properties: (a) replacing (thiophene)C-H with (thiazole)N reduces steric encumbrance in -BTzOR-Ar.06-0.25 cm2/(V s)) in organic thin-film transistors, as well as enhanced Ion:Ioff ratios and greater ambient stability than the BTOR analogues. These geometric and electronic properties make BTzOR a promising building block for new classes of polymer semiconductors, and the synthetic route to BTzOR reported here should be adaptable to many other bithiazole-based building blocks.",
author = "Xugang Guo and Jordan Quinn and Zhihua Chen and Hakan Usta and Yan Zheng and Yu Xia and Hennek, {Jonathan W.} and Ortiz, {Roc{\'i}o Ponce} and Marks, {Tobin J} and Antonio Facchetti",
year = "2013",
month = "2",
day = "6",
doi = "10.1021/ja3120532",
language = "English",
volume = "135",
pages = "1986--1996",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "5",

}

TY - JOUR

T1 - Dialkoxybithiazole

T2 - A new building block for head-to-head polymer semiconductors

AU - Guo, Xugang

AU - Quinn, Jordan

AU - Chen, Zhihua

AU - Usta, Hakan

AU - Zheng, Yan

AU - Xia, Yu

AU - Hennek, Jonathan W.

AU - Ortiz, Rocío Ponce

AU - Marks, Tobin J

AU - Facchetti, Antonio

PY - 2013/2/6

Y1 - 2013/2/6

N2 - Polymer semiconductors have received great attention for organic electronics due to the low fabrication cost offered by solution-based printing techniques. To enable the desired solubility/processability and carrier mobility, polymers are functionalized with hydrocarbon chains by strategically manipulating the alkylation patterns. Note that head-to-head (HH) linkages have traditionally been avoided because the induced backbone torsion leads to poor π-π overlap and amorphous film microstructures, and hence to low carrier mobilities. We report here the synthesis of a new building block for HH linkages, 4,4′-dialkoxy-5,5′-bithiazole (BTzOR), and its incorporation into polymers for high performance organic thin-film transistors. The small oxygen van der Waals radius and intramolecular S(thiazolyl) ⋯O(alkoxy) attraction promote HH macromolecular architectures with extensive π-conjugation, low bandgaps (1.40-1.63 eV), and high crystallinity. In comparison to previously reported 3,3′-dialkoxy-2,2′-bithiophene (BTOR), BTzOR is a promising building block in view of thiazole geometric and electronic properties: (a) replacing (thiophene)C-H with (thiazole)N reduces steric encumbrance in -BTzOR-Ar.06-0.25 cm2/(V s)) in organic thin-film transistors, as well as enhanced Ion:Ioff ratios and greater ambient stability than the BTOR analogues. These geometric and electronic properties make BTzOR a promising building block for new classes of polymer semiconductors, and the synthetic route to BTzOR reported here should be adaptable to many other bithiazole-based building blocks.

AB - Polymer semiconductors have received great attention for organic electronics due to the low fabrication cost offered by solution-based printing techniques. To enable the desired solubility/processability and carrier mobility, polymers are functionalized with hydrocarbon chains by strategically manipulating the alkylation patterns. Note that head-to-head (HH) linkages have traditionally been avoided because the induced backbone torsion leads to poor π-π overlap and amorphous film microstructures, and hence to low carrier mobilities. We report here the synthesis of a new building block for HH linkages, 4,4′-dialkoxy-5,5′-bithiazole (BTzOR), and its incorporation into polymers for high performance organic thin-film transistors. The small oxygen van der Waals radius and intramolecular S(thiazolyl) ⋯O(alkoxy) attraction promote HH macromolecular architectures with extensive π-conjugation, low bandgaps (1.40-1.63 eV), and high crystallinity. In comparison to previously reported 3,3′-dialkoxy-2,2′-bithiophene (BTOR), BTzOR is a promising building block in view of thiazole geometric and electronic properties: (a) replacing (thiophene)C-H with (thiazole)N reduces steric encumbrance in -BTzOR-Ar.06-0.25 cm2/(V s)) in organic thin-film transistors, as well as enhanced Ion:Ioff ratios and greater ambient stability than the BTOR analogues. These geometric and electronic properties make BTzOR a promising building block for new classes of polymer semiconductors, and the synthetic route to BTzOR reported here should be adaptable to many other bithiazole-based building blocks.

UR - http://www.scopus.com/inward/record.url?scp=84873365152&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84873365152&partnerID=8YFLogxK

U2 - 10.1021/ja3120532

DO - 10.1021/ja3120532

M3 - Article

VL - 135

SP - 1986

EP - 1996

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 5

ER -