Vinylene-bridged difluorobenzo[

C] [1,2,5]-thiadiazole (FBTzE): A new electron-deficient building block for high-performance semiconducting polymers in organic electronics

Yuya Asanuma, Hiroki Mori, Ryosuke Takahashi, Yasushi Nishihara

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

A new class of an acceptor unit, vinylene-bridged 5,6-difluorobenzothiadiazole FBTzE, has been developed. Palladium-catalyzed Migita-Kosugi-Stille coupling reactions of 1 with 2, yielding 3 and its sequential dehydrogenative coupling with 4, readily afforded FBTzE-containing monomers 5a-5c that have lower lowest unoccupied molecular orbital (LUMO) energy level and smaller energy gap than those of 5,6-difluorobenzothiadiazole (DFBT). Subsequently, three types of FBTzE-containing copolymers 3T, 4T, and 2TTT were synthesized by Migita-Kosugi-Stille coupling of monomers 5b and 5c with distannylated thiophene, bithiophene, and thienothiophene, respectively and their physicochemical properties and solar cell performances were evaluated. As a result of cyclic voltammogram, the synthesized FBTzE-based polymers have deeper highest occupied molecular orbital (HOMO) and LUMO energy levels, and stronger intermolecular interactions than those of DFBT-based polymer PffBT4T-DT. Although 3T/PC61BM blended film formed favorable face-on orientation with short dπ of 3.57 Å, its solar cell showed poor PCE of 2.7% owing to the construction of large phase separation structure with a domain size over 100 nm. In a sharp contrast, 2TTT/PC61BM formed unsuitable edge-on orientation with short dπ of 3.49 Å, but its film formed optimal nanoscale phase separation, leading to a good performance with PCE of up to 5.2%.

Original languageEnglish
Pages (from-to)905-916
Number of pages12
JournalJournal of Materials Chemistry C
Volume7
Issue number4
DOIs
Publication statusPublished - Jan 1 2019

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Thiadiazoles
Semiconducting polymers
Molecular orbitals
Electronic equipment
Phase separation
Electron energy levels
Electrons
Solar cells
Polymers
Monomers
Thiophenes
Palladium
Thiophene
Energy gap
Copolymers

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Chemistry

Cite this

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title = "Vinylene-bridged difluorobenzo[: C] [1,2,5]-thiadiazole (FBTzE): A new electron-deficient building block for high-performance semiconducting polymers in organic electronics",
abstract = "A new class of an acceptor unit, vinylene-bridged 5,6-difluorobenzothiadiazole FBTzE, has been developed. Palladium-catalyzed Migita-Kosugi-Stille coupling reactions of 1 with 2, yielding 3 and its sequential dehydrogenative coupling with 4, readily afforded FBTzE-containing monomers 5a-5c that have lower lowest unoccupied molecular orbital (LUMO) energy level and smaller energy gap than those of 5,6-difluorobenzothiadiazole (DFBT). Subsequently, three types of FBTzE-containing copolymers 3T, 4T, and 2TTT were synthesized by Migita-Kosugi-Stille coupling of monomers 5b and 5c with distannylated thiophene, bithiophene, and thienothiophene, respectively and their physicochemical properties and solar cell performances were evaluated. As a result of cyclic voltammogram, the synthesized FBTzE-based polymers have deeper highest occupied molecular orbital (HOMO) and LUMO energy levels, and stronger intermolecular interactions than those of DFBT-based polymer PffBT4T-DT. Although 3T/PC61BM blended film formed favorable face-on orientation with short dπ of 3.57 {\AA}, its solar cell showed poor PCE of 2.7{\%} owing to the construction of large phase separation structure with a domain size over 100 nm. In a sharp contrast, 2TTT/PC61BM formed unsuitable edge-on orientation with short dπ of 3.49 {\AA}, but its film formed optimal nanoscale phase separation, leading to a good performance with PCE of up to 5.2{\%}.",
author = "Yuya Asanuma and Hiroki Mori and Ryosuke Takahashi and Yasushi Nishihara",
year = "2019",
month = "1",
day = "1",
doi = "10.1039/c8tc05764h",
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TY - JOUR

T1 - Vinylene-bridged difluorobenzo[

T2 - C] [1,2,5]-thiadiazole (FBTzE): A new electron-deficient building block for high-performance semiconducting polymers in organic electronics

AU - Asanuma, Yuya

AU - Mori, Hiroki

AU - Takahashi, Ryosuke

AU - Nishihara, Yasushi

PY - 2019/1/1

Y1 - 2019/1/1

N2 - A new class of an acceptor unit, vinylene-bridged 5,6-difluorobenzothiadiazole FBTzE, has been developed. Palladium-catalyzed Migita-Kosugi-Stille coupling reactions of 1 with 2, yielding 3 and its sequential dehydrogenative coupling with 4, readily afforded FBTzE-containing monomers 5a-5c that have lower lowest unoccupied molecular orbital (LUMO) energy level and smaller energy gap than those of 5,6-difluorobenzothiadiazole (DFBT). Subsequently, three types of FBTzE-containing copolymers 3T, 4T, and 2TTT were synthesized by Migita-Kosugi-Stille coupling of monomers 5b and 5c with distannylated thiophene, bithiophene, and thienothiophene, respectively and their physicochemical properties and solar cell performances were evaluated. As a result of cyclic voltammogram, the synthesized FBTzE-based polymers have deeper highest occupied molecular orbital (HOMO) and LUMO energy levels, and stronger intermolecular interactions than those of DFBT-based polymer PffBT4T-DT. Although 3T/PC61BM blended film formed favorable face-on orientation with short dπ of 3.57 Å, its solar cell showed poor PCE of 2.7% owing to the construction of large phase separation structure with a domain size over 100 nm. In a sharp contrast, 2TTT/PC61BM formed unsuitable edge-on orientation with short dπ of 3.49 Å, but its film formed optimal nanoscale phase separation, leading to a good performance with PCE of up to 5.2%.

AB - A new class of an acceptor unit, vinylene-bridged 5,6-difluorobenzothiadiazole FBTzE, has been developed. Palladium-catalyzed Migita-Kosugi-Stille coupling reactions of 1 with 2, yielding 3 and its sequential dehydrogenative coupling with 4, readily afforded FBTzE-containing monomers 5a-5c that have lower lowest unoccupied molecular orbital (LUMO) energy level and smaller energy gap than those of 5,6-difluorobenzothiadiazole (DFBT). Subsequently, three types of FBTzE-containing copolymers 3T, 4T, and 2TTT were synthesized by Migita-Kosugi-Stille coupling of monomers 5b and 5c with distannylated thiophene, bithiophene, and thienothiophene, respectively and their physicochemical properties and solar cell performances were evaluated. As a result of cyclic voltammogram, the synthesized FBTzE-based polymers have deeper highest occupied molecular orbital (HOMO) and LUMO energy levels, and stronger intermolecular interactions than those of DFBT-based polymer PffBT4T-DT. Although 3T/PC61BM blended film formed favorable face-on orientation with short dπ of 3.57 Å, its solar cell showed poor PCE of 2.7% owing to the construction of large phase separation structure with a domain size over 100 nm. In a sharp contrast, 2TTT/PC61BM formed unsuitable edge-on orientation with short dπ of 3.49 Å, but its film formed optimal nanoscale phase separation, leading to a good performance with PCE of up to 5.2%.

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U2 - 10.1039/c8tc05764h

DO - 10.1039/c8tc05764h

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JO - Journal of Materials Chemistry C

JF - Journal of Materials Chemistry C

SN - 2050-7526

IS - 4

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