Synthesis and characterization of 3-(4-fluorophenyl)thieno[3,2-b]thiophene and 3,3’-(4- fluorophenyl)dithieno[3,2-b;2’,3’-d]thiophene molecules

Sema Topal; Sebahat Topal; Pelin Ulukan; Belkıs Ustamehmetoğlu; Turan Ozturk; Esma Sezer

doi:10.1016/j.electacta.2021.138837

Synthesis and characterization of 3-(4-fluorophenyl)thieno[3,2-b]thiophene and 3,3’-(4- fluorophenyl)dithieno[3,2-b;2’,3’-d]thiophene molecules

Sema Topal, Sebahat Topal, Pelin Ulukan, Belkıs Ustamehmetoğlu, Turan Ozturk, Esma Sezer^*

^*Corresponding author for this work

Department of Chemistry

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

10 Citations (Scopus)

Abstract

Synthesis of 3-(4-fluorophenyl)thieno[3,2-b]thiophene (FPhTT) and 3,3’-(4- fluorophenyl)dithieno[3,2-b;2’,3’-d]thiophene (FPhDTT) were achieved starting from 3-bromothiophene and 3,4-dibromothiophene, respectively. They were electropolymerized and the resulting polymers P[FPhTT] and P[FPhDTT] were characterized by diverse electrochemical methods such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge (GCD), electrochemical quartz crystal microbalance (EQCM) and spectroelectrochemical measurements. Mechanism of electropolymerization of the monomers was supported by DFT level calculations. Band gaps of P[FPhTT] and P[FPhDTT] were calculated as 1.63 and 1.77 eV, respectively, from the onset absorptions of the absorption spectra. From EIS measurements, the highest capacitance values of P[FPhTT] and P[FPhDTT] were calculated to be 39.4 and 281.7 Fg¹⁻, respectively, when the applied potentials were equal to their oxidation peak potentials. Surface characterization of the P[FPhTT] and P[FPhDTT] films on ITO electrodes were performed by atomic force microscope (AFM) and the results suggested that P[FPhDTT] had more porous surface. GCD results indicated that P[FPhDTT] had higher energy density than P[FPhTT], possibly due to its porous structure. According to the ECD results, P[FPhTT] has more stable optical properties. As a conclusion, P[FPhDTT] might be suggested for energy storage applications while P[FPhTT] could be suitable for electrochromic devices.

Original language	English
Article number	138837
Journal	Electrochimica Acta
Volume	390
DOIs	https://doi.org/10.1016/j.electacta.2021.138837
Publication status	Published - 10 Sept 2021

Bibliographical note

Publisher Copyright:
© 2021

Funding

In this work, TT and DTT structures possessing Ph group having strong electron-withdrawing F atom, FPhTT and FPhDTT , were synthesized, polymerized and characterized by electrochemical and spectrophotometric measurements. Electrochemical polymerization and molecular orbitals of the monomers were supported by DFT calculations using Gaussian 09 program. Morphological properties of P[FPhTT] and P[FPhDTT] films on ITO electrodes were characterized by AFM. We thank The Scientific and Technological Research Council of Turkey (TUBITAK) for grants to Sebahat Topal and Sema Topal (TUBITAK BIDEB 2211A), and also thank The Higher Education Council of Turkey (YOK) (Ph.D. 100/2000 YOK) for for grants to Sebahat Topal. In addition, we would like to thank Istanbul Technical University Scientific Research Projects (Project No: 42325) and Unsped Global Logistics for their financial support. We are indebted to National Center for High Performance Computing (UHeM) under grant number <4007702020> (Sebahat Topal project: editmb) for the computational chemistry studies.

Funders	Funder number
Higher Education Council of Turkey	100/2000 YOK
National Center for High Performance Computing
TUBITAK	BIDEB 2211A
YOK
Ulusal Yüksek Başarımlı Hesaplama Merkezi, Istanbul Teknik Üniversitesi
Türkiye Bilimsel ve Teknolojik Araştirma Kurumu
Istanbul Teknik Üniversitesi	42325

Keywords

3,3’-(4-Fluorophenyl)dithieno[3,2-b;2’,3’-d]thiophene
3-(4-Fluorophenyl)thieno[3,2-b]thiophene
Capacitive and electrochromic behavior
DFT
EQCM
Electropolymerization

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10.1016/j.electacta.2021.138837

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@article{a328cb0fff4f4a569347f7d572ee0cd4,

title = "Synthesis and characterization of 3-(4-fluorophenyl)thieno[3,2-b]thiophene and 3,3{\textquoteright}-(4- fluorophenyl)dithieno[3,2-b;2{\textquoteright},3{\textquoteright}-d]thiophene molecules",

abstract = "Synthesis of 3-(4-fluorophenyl)thieno[3,2-b]thiophene (FPhTT) and 3,3{\textquoteright}-(4- fluorophenyl)dithieno[3,2-b;2{\textquoteright},3{\textquoteright}-d]thiophene (FPhDTT) were achieved starting from 3-bromothiophene and 3,4-dibromothiophene, respectively. They were electropolymerized and the resulting polymers P[FPhTT] and P[FPhDTT] were characterized by diverse electrochemical methods such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge (GCD), electrochemical quartz crystal microbalance (EQCM) and spectroelectrochemical measurements. Mechanism of electropolymerization of the monomers was supported by DFT level calculations. Band gaps of P[FPhTT] and P[FPhDTT] were calculated as 1.63 and 1.77 eV, respectively, from the onset absorptions of the absorption spectra. From EIS measurements, the highest capacitance values of P[FPhTT] and P[FPhDTT] were calculated to be 39.4 and 281.7 Fg1−, respectively, when the applied potentials were equal to their oxidation peak potentials. Surface characterization of the P[FPhTT] and P[FPhDTT] films on ITO electrodes were performed by atomic force microscope (AFM) and the results suggested that P[FPhDTT] had more porous surface. GCD results indicated that P[FPhDTT] had higher energy density than P[FPhTT], possibly due to its porous structure. According to the ECD results, P[FPhTT] has more stable optical properties. As a conclusion, P[FPhDTT] might be suggested for energy storage applications while P[FPhTT] could be suitable for electrochromic devices.",

keywords = "3,3{\textquoteright}-(4-Fluorophenyl)dithieno[3,2-b;2{\textquoteright},3{\textquoteright}-d]thiophene, 3-(4-Fluorophenyl)thieno[3,2-b]thiophene, Capacitive and electrochromic behavior, DFT, EQCM, Electropolymerization",

author = "Sema Topal and Sebahat Topal and Pelin Ulukan and Belkıs Ustamehmetoğlu and Turan Ozturk and Esma Sezer",

note = "Publisher Copyright: {\textcopyright} 2021",

year = "2021",

month = sep,

day = "10",

doi = "10.1016/j.electacta.2021.138837",

language = "English",

volume = "390",

journal = "Electrochimica Acta",

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T1 - Synthesis and characterization of 3-(4-fluorophenyl)thieno[3,2-b]thiophene and 3,3’-(4- fluorophenyl)dithieno[3,2-b;2’,3’-d]thiophene molecules

AU - Topal, Sema

AU - Topal, Sebahat

AU - Ulukan, Pelin

AU - Ustamehmetoğlu, Belkıs

AU - Ozturk, Turan

AU - Sezer, Esma

PY - 2021/9/10

Y1 - 2021/9/10

N2 - Synthesis of 3-(4-fluorophenyl)thieno[3,2-b]thiophene (FPhTT) and 3,3’-(4- fluorophenyl)dithieno[3,2-b;2’,3’-d]thiophene (FPhDTT) were achieved starting from 3-bromothiophene and 3,4-dibromothiophene, respectively. They were electropolymerized and the resulting polymers P[FPhTT] and P[FPhDTT] were characterized by diverse electrochemical methods such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge (GCD), electrochemical quartz crystal microbalance (EQCM) and spectroelectrochemical measurements. Mechanism of electropolymerization of the monomers was supported by DFT level calculations. Band gaps of P[FPhTT] and P[FPhDTT] were calculated as 1.63 and 1.77 eV, respectively, from the onset absorptions of the absorption spectra. From EIS measurements, the highest capacitance values of P[FPhTT] and P[FPhDTT] were calculated to be 39.4 and 281.7 Fg1−, respectively, when the applied potentials were equal to their oxidation peak potentials. Surface characterization of the P[FPhTT] and P[FPhDTT] films on ITO electrodes were performed by atomic force microscope (AFM) and the results suggested that P[FPhDTT] had more porous surface. GCD results indicated that P[FPhDTT] had higher energy density than P[FPhTT], possibly due to its porous structure. According to the ECD results, P[FPhTT] has more stable optical properties. As a conclusion, P[FPhDTT] might be suggested for energy storage applications while P[FPhTT] could be suitable for electrochromic devices.

AB - Synthesis of 3-(4-fluorophenyl)thieno[3,2-b]thiophene (FPhTT) and 3,3’-(4- fluorophenyl)dithieno[3,2-b;2’,3’-d]thiophene (FPhDTT) were achieved starting from 3-bromothiophene and 3,4-dibromothiophene, respectively. They were electropolymerized and the resulting polymers P[FPhTT] and P[FPhDTT] were characterized by diverse electrochemical methods such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge (GCD), electrochemical quartz crystal microbalance (EQCM) and spectroelectrochemical measurements. Mechanism of electropolymerization of the monomers was supported by DFT level calculations. Band gaps of P[FPhTT] and P[FPhDTT] were calculated as 1.63 and 1.77 eV, respectively, from the onset absorptions of the absorption spectra. From EIS measurements, the highest capacitance values of P[FPhTT] and P[FPhDTT] were calculated to be 39.4 and 281.7 Fg1−, respectively, when the applied potentials were equal to their oxidation peak potentials. Surface characterization of the P[FPhTT] and P[FPhDTT] films on ITO electrodes were performed by atomic force microscope (AFM) and the results suggested that P[FPhDTT] had more porous surface. GCD results indicated that P[FPhDTT] had higher energy density than P[FPhTT], possibly due to its porous structure. According to the ECD results, P[FPhTT] has more stable optical properties. As a conclusion, P[FPhDTT] might be suggested for energy storage applications while P[FPhTT] could be suitable for electrochromic devices.

KW - 3,3’-(4-Fluorophenyl)dithieno[3,2-b;2’,3’-d]thiophene

KW - 3-(4-Fluorophenyl)thieno[3,2-b]thiophene

KW - Capacitive and electrochromic behavior

KW - DFT

KW - EQCM

KW - Electropolymerization

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DO - 10.1016/j.electacta.2021.138837

M3 - Article

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SN - 0013-4686

VL - 390

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JF - Electrochimica Acta

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ER -

Synthesis and characterization of 3-(4-fluorophenyl)thieno[3,2-b]thiophene and 3,3’-(4- fluorophenyl)dithieno[3,2-b;2’,3’-d]thiophene molecules

Abstract

Bibliographical note

Funding

Keywords

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