Electropolymers of 4-(thieno[3,2-b]thiophen-3-yl)benzonitrile extended with thiophene, 3-hexylthiophene and EDOT moieties; their electrochromic applications

Ilknur Demirtas; Erdal Ertas; Sebahat Topal; Turan Ozturk

doi:10.1016/j.polymer.2021.124286

Electropolymers of 4-(thieno[3,2-b]thiophen-3-yl)benzonitrile extended with thiophene, 3-hexylthiophene and EDOT moieties; their electrochromic applications

Ilknur Demirtas, Erdal Ertas, Sebahat Topal, Turan Ozturk^*

^*Corresponding author for this work

Department of Chemistry

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

13 Citations (Scopus)

Abstract

Three new π-conjugated 4-(thieno[3,2-b]thiophen-3-yl)benzonitrile based monomers having thiophene, 3-hexylthiophene and EDOT at the peripherals were synthesized. Their electropolymerization produced the corresponding electroactive polymers, P1, P2, and P3, which exhibited electrochromic properties with color developments from red to blue, orange-yellow to pale-blue, and purple to pale-grey, respectively. Functional design of the monomers with electron deficient benzonitrile at ß-position of thieno[3,2-b]thiophene (TT) and electron-rich thienyl groups at the peripherals influenced the HOMO and LUMO levels and, thereby, reduced the band gap of the conjugated polymers. Considering the band gaps of electropolymerized TT based polymers in the literature, the polymer P3, obtained through electropolymerization, had a comparable band gap of 1.73 eV. Electrochromic devices (ECD) of the new polymers displayed different optical contrasts (ΔT%) of 20% at 507 nm, 25% at 443 nm, and 34% at 579 nm for P1/PProDOP, P2/PProDOP, and P3/PProDOP, respectively. Furthermore, they had modest switch times of 1.2–1.7 s for bleaching and 0.9–1.7 s for coloring. Of the polymers, P3/PProDOP, bearing EDOT moieties, had a reasonable coloration efficiency (CE) of 240 cm²/C at 579 nm, excellent permanent memory effect, and high stability of color switch, retaining 88% of its electroactivity after 500 cycles, switching at the applied voltages of −0.2 and + 1.1 V.

Original language	English
Article number	124286
Journal	Polymer
Volume	235
DOIs	https://doi.org/10.1016/j.polymer.2021.124286
Publication status	Published - 19 Nov 2021

Bibliographical note

Publisher Copyright:
© 2021 Elsevier Ltd

Funding

Colored polymer films were produced on ITO-coated glass electrodes under potentiodynamic conditions, using a Pt disk as a counter electrode and an Ag wire as a pseudo reference electrode, NaClO4/LiClO4 (0.1 mol L−1) as a supporting electrolyte in ACN, while the monomer concentrations were kept at 1 mmol L−1 3,4-Propylenedioxypyrrole (PProDOP) was used as a counter electrode [40]; similarly, it was dissolved in ACN-LiClO4 (0.1 mol L−1) system, and polymerized potentiodynamically onto an ITO-coated glass electrode. ACN/PC/PMMA/LiClO4:70/20/7/3 by weight [41] was used to prepare a transparent and conducting gel electrolyte. The gel electrolyte was applied onto the counter electrolyte while it was kept at its oxidized state. The ECD was constructed by sandwiching two polymer films (one oxidized and the other reduced), keeping them separate with a gel electrolyte.We thank the Scientific and Technological Research Council of Turkey, Ankara, Turkey (TUBITAK, grant 214Z297) and Istanbul Technical University, Istanbul, Turkey (ITU, grant 39356) for the financial supports. We thank the Higher Education Council of Turkey, Ankara, Turkey (YOK), and TUBITAK, Ankara, Turkey for grants to Sebahat Topal (Ph.D. 100/2000 YOK, and TUBITAK BIDEB 2211A). We are indebted to the National Center for High Performance Computing of Turkey, Istanbul, Turkey (UHeM) under grant number 4007702020 (Sebahat Topal project: editmb). We also thank to the Unsped Global Lojistik, Istanbul, Turkey for financial supports. We thank the Scientific and Technological Research Council of Turkey, Ankara, Turkey (TUBITAK, grant 214Z297 ) and Istanbul Technical University, Istanbul, Turkey (ITU, grant 39356 ) for the financial supports. We thank the Higher Education Council of Turkey, Ankara, Turkey (YOK) , and TUBITAK, Ankara, Turkey for grants to Sebahat Topal (Ph.D., 100/2000 YOK, and TUBITAK BIDEB 2211A). We are indebted to the National Center for High Performance Computing of Turkey, Istanbul, Turkey (UHeM) under grant number 4007702020 (Sebahat Topal project: editmb). We also thank to the Unsped Global Lojistik, Istanbul, Turkey for financial supports.

Funders	Funder number
Higher Education Council of Turkey	100/2000 YOK, BIDEB 2211A
Istanbul Technical University, Istanbul, Turkey
Scientific and Technological Research Council of Turkey, Ankara, Turkey
International Technological University	39356
Ulusal Yüksek Başarımlı Hesaplama Merkezi, Istanbul Teknik Üniversitesi	4007702020
Türkiye Bilimsel ve Teknolojik Araştirma Kurumu	214Z297

Keywords

Donor-acceptor
Electrochromic device
Electrochromic polymer
Thienothiophene

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10.1016/j.polymer.2021.124286

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title = "Electropolymers of 4-(thieno[3,2-b]thiophen-3-yl)benzonitrile extended with thiophene, 3-hexylthiophene and EDOT moieties; their electrochromic applications",

abstract = "Three new π-conjugated 4-(thieno[3,2-b]thiophen-3-yl)benzonitrile based monomers having thiophene, 3-hexylthiophene and EDOT at the peripherals were synthesized. Their electropolymerization produced the corresponding electroactive polymers, P1, P2, and P3, which exhibited electrochromic properties with color developments from red to blue, orange-yellow to pale-blue, and purple to pale-grey, respectively. Functional design of the monomers with electron deficient benzonitrile at {\ss}-position of thieno[3,2-b]thiophene (TT) and electron-rich thienyl groups at the peripherals influenced the HOMO and LUMO levels and, thereby, reduced the band gap of the conjugated polymers. Considering the band gaps of electropolymerized TT based polymers in the literature, the polymer P3, obtained through electropolymerization, had a comparable band gap of 1.73 eV. Electrochromic devices (ECD) of the new polymers displayed different optical contrasts (ΔT%) of 20% at 507 nm, 25% at 443 nm, and 34% at 579 nm for P1/PProDOP, P2/PProDOP, and P3/PProDOP, respectively. Furthermore, they had modest switch times of 1.2–1.7 s for bleaching and 0.9–1.7 s for coloring. Of the polymers, P3/PProDOP, bearing EDOT moieties, had a reasonable coloration efficiency (CE) of 240 cm2/C at 579 nm, excellent permanent memory effect, and high stability of color switch, retaining 88% of its electroactivity after 500 cycles, switching at the applied voltages of −0.2 and + 1.1 V.",

keywords = "Donor-acceptor, Electrochromic device, Electrochromic polymer, Thienothiophene",

author = "Ilknur Demirtas and Erdal Ertas and Sebahat Topal and Turan Ozturk",

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year = "2021",

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doi = "10.1016/j.polymer.2021.124286",

language = "English",

volume = "235",

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T1 - Electropolymers of 4-(thieno[3,2-b]thiophen-3-yl)benzonitrile extended with thiophene, 3-hexylthiophene and EDOT moieties; their electrochromic applications

AU - Demirtas, Ilknur

AU - Ertas, Erdal

AU - Topal, Sebahat

AU - Ozturk, Turan

PY - 2021/11/19

Y1 - 2021/11/19

N2 - Three new π-conjugated 4-(thieno[3,2-b]thiophen-3-yl)benzonitrile based monomers having thiophene, 3-hexylthiophene and EDOT at the peripherals were synthesized. Their electropolymerization produced the corresponding electroactive polymers, P1, P2, and P3, which exhibited electrochromic properties with color developments from red to blue, orange-yellow to pale-blue, and purple to pale-grey, respectively. Functional design of the monomers with electron deficient benzonitrile at ß-position of thieno[3,2-b]thiophene (TT) and electron-rich thienyl groups at the peripherals influenced the HOMO and LUMO levels and, thereby, reduced the band gap of the conjugated polymers. Considering the band gaps of electropolymerized TT based polymers in the literature, the polymer P3, obtained through electropolymerization, had a comparable band gap of 1.73 eV. Electrochromic devices (ECD) of the new polymers displayed different optical contrasts (ΔT%) of 20% at 507 nm, 25% at 443 nm, and 34% at 579 nm for P1/PProDOP, P2/PProDOP, and P3/PProDOP, respectively. Furthermore, they had modest switch times of 1.2–1.7 s for bleaching and 0.9–1.7 s for coloring. Of the polymers, P3/PProDOP, bearing EDOT moieties, had a reasonable coloration efficiency (CE) of 240 cm2/C at 579 nm, excellent permanent memory effect, and high stability of color switch, retaining 88% of its electroactivity after 500 cycles, switching at the applied voltages of −0.2 and + 1.1 V.

AB - Three new π-conjugated 4-(thieno[3,2-b]thiophen-3-yl)benzonitrile based monomers having thiophene, 3-hexylthiophene and EDOT at the peripherals were synthesized. Their electropolymerization produced the corresponding electroactive polymers, P1, P2, and P3, which exhibited electrochromic properties with color developments from red to blue, orange-yellow to pale-blue, and purple to pale-grey, respectively. Functional design of the monomers with electron deficient benzonitrile at ß-position of thieno[3,2-b]thiophene (TT) and electron-rich thienyl groups at the peripherals influenced the HOMO and LUMO levels and, thereby, reduced the band gap of the conjugated polymers. Considering the band gaps of electropolymerized TT based polymers in the literature, the polymer P3, obtained through electropolymerization, had a comparable band gap of 1.73 eV. Electrochromic devices (ECD) of the new polymers displayed different optical contrasts (ΔT%) of 20% at 507 nm, 25% at 443 nm, and 34% at 579 nm for P1/PProDOP, P2/PProDOP, and P3/PProDOP, respectively. Furthermore, they had modest switch times of 1.2–1.7 s for bleaching and 0.9–1.7 s for coloring. Of the polymers, P3/PProDOP, bearing EDOT moieties, had a reasonable coloration efficiency (CE) of 240 cm2/C at 579 nm, excellent permanent memory effect, and high stability of color switch, retaining 88% of its electroactivity after 500 cycles, switching at the applied voltages of −0.2 and + 1.1 V.

KW - Donor-acceptor

KW - Electrochromic device

KW - Electrochromic polymer

KW - Thienothiophene

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DO - 10.1016/j.polymer.2021.124286

M3 - Article

AN - SCOPUS:85118276972

SN - 0032-3861

VL - 235

JO - Polymer

JF - Polymer

M1 - 124286

ER -

Electropolymers of 4-(thieno[3,2-b]thiophen-3-yl)benzonitrile extended with thiophene, 3-hexylthiophene and EDOT moieties; their electrochromic applications

Abstract

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Keywords

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