Electrochimica Acta 390 (2021) 138837

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

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 a, Sebahat Topal a, Pelin Ulukan a, Belkıs Ustamehmetoğlu a, Turan Ozturk a,b,
Esma Sezer a,∗
a
Istanbul Technical University, Department of Chemistry, 34469 Maslak, Istanbul, Turkey
b
TUBITAK-UME, Chemistry Group Laboratories, PO Box 54, 41471 Gebze, Kocaeli, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: Synthesis of 3-(4-fluorophenyl)thieno[3,2-b]thiophene (FPhTT) and 3,3’-(4- fluorophenyl)dithieno[3,2-

Received 5 January 2021 b;2’,3’-d]thiophene (FPhDTT) were achieved starting from 3-bromothiophene and 3,4-dibromothiophene,
Revised 14 June 2021
respectively. They were electropolymerized and the resulting polymers P[FPhTT] and P[FPhDTT] were
Accepted 21 June 2021
characterized by diverse electrochemical methods such as cyclic voltammetry (CV), electrochemical
Available online 25 June 2021
impedance spectroscopy (EIS), galvanostatic charge-discharge (GCD), electrochemical quartz crystal mi-
Keywords: crobalance (EQCM) and spectroelectrochemical measurements. Mechanism of electropolymerization of
3-(4-Fluorophenyl)thieno[3,2-b]thiophene the monomers was supported by DFT level calculations. Band gaps of P[FPhTT] and P[FPhDTT] were cal-
3,3’-(4-Fluorophenyl)dithieno[3,2-b;2’,3’- culated as 1.63 and 1.77 eV, respectively, from the onset absorptions of the absorption spectra. From EIS
d]thiophene measurements, the highest capacitance values of P[FPhTT] and P[FPhDTT] were calculated to be 39.4 and
Electropolymerization 281.7 Fg1− , respectively, when the applied potentials were equal to their oxidation peak potentials. Sur-
Capacitive and electrochromic behavior
face characterization of the P[FPhTT] and P[FPhDTT] films on ITO electrodes were performed by atomic
EQCM
DFT
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.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction are advantageous with lower band gap, extended π conjugation,

Conductive polymers (CPs), which were ground-breaking with
their discoveries in the literature, have become the focus of many
researchers in recent years, finding applications in wide range
of areas as they can be obtained by chemical and electrochem-
ical methods and their properties can be improved with differ-
ent functional groups [1–3]. Polyaniline (PANI), polyacetylene (PA),
polythiophene (PTh), polyphenylene (PPh), polypyrol (PPy), polyfu-
ran (PFu), poly(vinyl chloride) (PVC), poly(para-phenylene) (PPP),
polyvinyl and polyindole (PVIn) are the examples of commonly
used organic CPs in the literature [4]. Thiophene (Th)-based con-
ducting polymers have been holding a particular interest, owing
to their environmental stability, high charge carrier mobility, low
cost and flexibility [5–10]. In the polymer form, fused Th rings
∗
Corresponding author.
E-mail address: esezer@itu.edu.tr (E. Sezer).
flat structure and high mobility on carrying charge compared to
Th [11–13]. In electronic and optoelectronic material chemistry,
thienothiophenes (TT) and dithienothiophenes (DTT) are attrac-
tive heterocyclic compounds due to their electron rich structures
generated by two and three sulfur atoms in the rings, respec-
tively, and planarity [14–16]. Generally, TT and DTT are used as
donors, π -bridges and π -π -packing agents in designed organic
small molecules and polymers for organic light emitting diods
(OLED), solar cells, electrochromic devices (ECD), transistors and
capacitors etc [17–22].
By para-substitution with phenyl(Ph) groups at C-3 position
of TT and obtaining 3-phenylthieno[3,2-b]thiophene (PhTT) [12],
properties of TT for applications could be improved and become
promising p-type organic semiconductors.
The addition of heteroatoms onto the polymer backbone could
be effective way to improve the electrochemical, morphological,
and optical performance. The fluorine (F) atom is the excellent
alternative to enhance the polymer performance due to strong

https://doi.org/10.1016/j.electacta.2021.138837
0013-4686/© 2021 Elsevier Ltd. All rights reserved.
S. Topal, S. Topal, P. Ulukan et al.
Scheme 1. General synthesis of FPhTT and FPhDTT.
electron affinity, small atomic radius [23]. There are some exam-
ple about that the fluorine substituted organic compounds en-
hance the performance of organic electronic material as improving
air stability, color stability and enhancing the conjugation due to
more planarity than non-fluorinated groups [24–27]. In our previ-
ous study, PhTT and Ph2 DTT were electropolymerized, character-
ized and results suggested that P[PhTT] and P[Ph2 DTT] were good
candidate for optical and electronic applications [28,29].
In this work, TT and DTT structures possessing Ph group hav-
ing 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 charac-
terized by AFM.
2. General design and synthesis of monomers
Synthesis of the monomers 3-(4-fluorophenyl)thieno[3,2-
b]thiophene, FPhTT and 3,5-bis(4-fluorophenyl)dithieno[3,2-
b:2 ,3 -d]thiophene, FPhDTT were achieved following the
method developed by our group [12,17,30]. Lithiation of 3-
bromothiophene with n-BuLi was followed by addition of (i) S8
and (ii) 2-bromo-4 -fluoroacetophenone leading to the forma-
tion of (1-(4-fluorophenyl)-2-(thiophene-3-ylthio)ethanone) (MK)
in 86% yield (Scheme 1). Then, in presence of polyphosphoric
acid (PPA) in chlorobenzene, MK was converted to the corre-
sponding FPhTT in 84% yield [31,32]. Regarding the synthesis
of FPhDTT, initially the diketone (DK), (2,2 -(thiophene-3,4-
diylbis(sulfanediyl))bis(1-(4-fluorophenyl)ethanone)) was synthe-
sized by lithiation of, 3,4-dibromothiophene, this time, with t-BuLi,
which was followed by addition of (i) S8 and then (ii) 2-bromo-
4 -fluoroacetophenone to produce DK in 58% yield. Similarly, its
reaction in the presence of PPA in chlorobenzene produced 3,5-
bis(4-fluorophenyl)dithieno[3,2-b:2 ,3 -d]thiophene, FPhDTT in 70%
yield (Scheme 1). Details of the syntheses and characterizations
are given in supporting information (Figure S1-S5).
2.1. Electrochemical polymerization of FPhTT and FPhDTT
Electrochemical polymerizations of the monomers were per-
formed in a standard three electrodes system, using a spiral plat-
inum wire as a counter electrode, a silver wire as a pseudo-
reference electrode, and a GC bottom electrode (area = 0.022 cm2 )
as a working electrode, to provide a better polymerization stability
and deposition on the electrode surface. Potentiodynamic method
was used to obtain P[FPhTT] and P[FPhDTT] films on the electrode
2
Electrochimica Acta 390 (2021) 138837
surface at a scan rate of 100 mV s−1 by applying 15 cycles in anhy-
drous ACN/DCM, 3/1 v/v, containing 0.1 M Bu4 NPF6 as a supporting
electrolyte under ambient conditions.
Due to the presence of fluorine as an electron-withdrawing
atom, oxidation onsets of FPhTT and FPhDTT appeared at 1.35 V
and 1.17 V, respectively, which were higher than the potentials of
non-fluorine analogues, i.e. PhTT (1.26 V) and PhDTT (0.56 V) [28,
29]. In repetitive cycles, a regular increase was observed in peak
currents (Figure 1) and orange and brown colored polymer films
of P[FPhTT] and P[FPhDTT], respectively, were electrodeposited on
the electrode surface. The last deposition cycles (15th ) of the poly-
mers films (Fig. 1 a and b) indicated that the anodic current of
P[FPhTT] (0.02 mA at 1.2 V) was four times lower than the value
of P[FPhDTT] (0.08 mA at 1.1 V).
2.2. Investigation of redox behaviors of P[FPhTT] and P[FPhDTT] films
by CV
The redox behaviors of P[FPhTT] and P[FPhDTT] films were
examined by CV in 0.1 M Bu4 NPF6 /ACN at different scan rates
(Fig. 2). The CV measurements were performed in the range of 0.0-
1.7 V and 0.0-1.5 V for P[FPhTT] and P[FPhDTT], respectively. Ox-
idation onsets of P[FPhTT] and P[FPhDTT] were found as 0.70 V
and 1.08 V, respectively which were lower than their correspond-
ing monomers as expected due to increase in conjugation length.
While P[FPhTT] had two reversible anodic and cathodic peaks at
0.9 and 1.4 V, P[FPhDTT] showed semi-reversible anodic and ca-
thodic peaks at 1.2 and 1.0 V, respectively.
A steady increase at the peak currents with the scan rates for
both polymers was observed, while the peak potentials mainly re-
mained unchanged even at 20 0 0 mVs−1 for P[FPhTT] (Fig. S7). On
the other hand, P[FPhDTT] film displayed a shift in the peak to
more anodic potential at higher scan rates than 300 mVs−1 pos-
sibly due to slower electron transfer reaction. The main reason for
this is obtaining higher film thickness of P[FPhDTT] than P[FPhTT]
at the same number of deposition cycles. As the film thickness in-
creases, diffusion become difficult [33]. This makes the CV as semi-
reversible or irreversible.
CVs of FPhTT and FPhDTT obtained during the polymerizations
(1st cycle) and the polymer films at 300 mVs−1 were depicted in
Fig. 3, which indicated that fusing another Th ring to TT (FPhDTT)
resulted in, as expected, a decrease in the oxidation potential due
to the increase in conjugation.
Previous studies showed that the mass and thickness of a film
increase proportional to the number of cycles [34,35], and the
polymer film thickness can be estimated through the mass of poly-
mers.
S. Topal, S. Topal, P. Ulukan et al. Electrochimica Acta 390 (2021) 138837

Fig. 1. CVs for the polymerization of FPhTT (a) in ACN and FPhDTT (b) in ACN/DCM, 3/1 v/v containing 0.1 M Bu4 NPF6 , on GC electrode by applying 100 mV/s.

Fig. 2. CVs of P[FPhTT] (a) and P[FPhDTT] (b) films obtained at different scan rates in ACN containing 0.1 M Bu4 NPF6 .

Fig. 3. Comparison of first cycles of FPhTT and FPhDTT during electrochemical polymerizations (a) and CVs of P[FPhTT] and P[FPhDTT] films (b).

Active masses (m) of the polymer films on the electrode surface
were calculated according to the modified Faraday’s law (1) [1]:
Q Mm + γ × Md
m= × (1)
F (2 + γ )
Where Mm and Md are the molecular weights of the monomer
and dopant, respectively, and γ is the doping degree, which was
assumed to be 0.25 for both monomers as suggested in litera-
ture [36–38]. In the light of this information, the mass of the
P[FPhDTT] film, formed on the surface, was found to be 7.5 times
higher than the mass of P[FPhTT], and consequently, P[FPhDTT]
was found to have higher thickness, which also means higher sur-
face area. This result explained the reason of higher current densi-
ties of P[FPhDTT] (Fig. 3b).
Scan rates and the square root of scan rates versus anodic and
cathodic peak currents were plotted (Fig. S8 and S9). Regression
coefficients (R2 ) were calculated to be higher for Ip -scan rate plot
of P[FPhTT] and Ip -(scan rate)1/2 plot of P[FPhTT], which indicated
that P[FPhTT] and P[FPhTT] had thin film behavior and diffusion
control mechanism, respectively [39].
Power law dependence of the peak current (Ip ) on scan rate
(ν ) is given in Eq. (2) [40], where the slope (b) is 1.0 for capaci-
tive materials and 0.5 for typical battery-type materials. Although
a clear boundary is not easy to define, the materials such as CPs
having “transition” area between capacitive and battery type be-
haviors and defined as pseudocapacitive are located in the range
of 0.5–1.0.
log l p = log a + b log v (2)
P[FPhTT] showed capacitive and pseudocapacitive properties
with a slopes of 1 at Epa = 0.9 V and 0.86 at Epa =1.4 V respec-
tively (Fig. 4a). On the other hand, P[FPhDTT] had a battery-type
diffusion-controlled intercalation processes [40] as it had a slope
of 0.23 at Epa =1.2 V (Fig. 4b).

3
S. Topal, S. Topal, P. Ulukan et al. Electrochimica Acta 390 (2021) 138837

Fig. 4. The relationship between log(anodic current) and log(scan rate) at Epa = 0.9 V and Epa = 1.4 V for P[FPhTT] (a) and at Epa = 1.2 V for P[FPhDTT] (b).

Fig. 5. Nyquist (a,b) and Phase angle plots (c,d) of P[FPhTT] (a,c) and P[FPhDTT] (b,d) films on GC electrode at different potentials.

Table 1
CLF values of P[FPhTT] and P[FPhDTT] at different EDC s.

Potential, (V) 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

CLF, (F/g) P[FPhTT] 2.7 5 7.6 8.6 13.4 28 19.5 39.3

P[FPhDTT] 5.6 8 7.5 11 12 147.2 281.7 192

2.3. EIS results
EIS measurements of P[FPhTT] and P[FPhDTT] films were con-
ducted applying different potentials (EDC ) in a wide frequency
range (10 mHz-10 MHz) in 0.1 M Bu4 NPF6 /ACN supporting elec-
trolyte. Nyquist and Bode graphs (Fig. 5 and Fig. S10) showed
a decrease in resistances with an increase in potentials for the
both polymers, and as the potential increased the phase angle ap-
proached to 90° in the low frequency region.
For the charge storage analysis of P[FPhTT] and P[FPhDTT],
low-frequency capacitance values (CLF ) were calculated using the
Eq. (3) [41–43], and the results were given in Table 1:
1 sulting from the interaction at the electrolyte and electrode inter-
CLF =
2π f Zim m
Where f is the frequency, Zim is the imaginary part of
impedance and m is the active mass of the polymer, which was
calculated using Eq. (1).
When the CLF values were placed on the same graph with the
CVs of the polymers (Fig. 6), the CLF increased with EDC up to the
oxidation potential. There are two main reasons for the increase of
CLF of the polymers with the increase of the applied potential. Ini-
tially, the polymer was oxidized, becoming charged and more con-
ductive, which increased the dielectric constant. Then, as the poly-
mer was positively charged with the increase in potential, anions
entered into the chain from the electrolyte to maintain a charge
balance. Thus, the polymer became swelled. The capacitance re-
(3) face started to increase due to the increasing surface area with the

4
S. Topal, S. Topal, P. Ulukan et al.
Fig. 6. CLF values at different EDC s and CVs of P[FPhTT] (a) and P[FPhDTT] (b) films, obtained at different scan rates in ACN containing 0.1 M Bu4 NPF6 .
Fig. 7. Equivalent circuit models of P[FPhTT] (a) and P[FPhDTT] (b).
anion inclusion into the polymer. In this way, capacitance of the
swollen polymer increased demonstrating a maximum value at Epa
[44].
2.4. Equivalent circuit models
Equivalent circuit modeling studies were performed using 1.0
V impedance data for P[FPhTT] and P[FPhDTT] films. Bode curves
of P[FPhTT] and P[FPhDTT], obtained from experimental (point)
and simulated (straight line) data from the equivalent circuit, were
given in Fig. S11 and they are in good agrements with each other.
Impedance results of P[FPhTT] were explained with a simple cir-
cuit similar to the Randles cell (Fig. 7a) with the best fitting (Chi
square, χ 2 = 9.76 × 10−4 ) and all the circuit values were summa-
rized in Table S1. In this circuit, Rs represents the resistance of the
electrolyte and Q is the constant phase element, arising from non-
ideal behavior of interface between the electrode and electrolyte.
The Warburg (W) element was added to the circuit to provide the
system with an additional resistance due to ion diffusion. Ce and
Re represent the capacitance and resistance of the bare electrode,
respectively.
The model given in Fig. 7b was designed for P[FPhDTT], by us-
ing the circuit model previously suggested for P[PhDTT] [28]. All
the parameters obtained from the circuit model with the best fit-
ting (χ 2 = 9.0 × 10−4 ) were given in Table S2. In this circuit, Rs
is the solution resistance, C1 and Rct are the charge transfer capac-
itance and resistance, respectively. The C3 , C4 and the resistances
between R2 and R4 are the elements for electrical behavior of the
polymer film due to its porous structure. Q1 and Q2 refer to con-
stant phase elements in the circuit and represent the heterogeneity
of the surface of the electrode.
2.5. EQCM measurements
EQCM measurements were performed by using Autolab EQCM
kit. A gold-plated quartz electrode was used as a working elec-
trode (area = 0.361 cm2 , crystalline sensitivity factor, Cf = 0.0815
Hz·ng−1 ·cm−2 for a 6 MHz at 20 °C), a spiral-shaped gold wire was
used as a counter electrode, and an Ag/AgCl was applied as a ref-
erence electrode.
According to the Sauerbrey Eq. [45], the frequency (f) decreases
as the mass (m) of a polymer deposited on the surface increases
(Eq. 4). The frequency changes (f) were monitored during the
polymerization of FPhTT and FPhDTT to detect the active mass
5
Electrochimica Acta 390 (2021) 138837
changes (m) of their corresponding polymers, deposited on the
electrode surface, and explain the mechanism of the polymeriza-
tion.
f
m = − (4)
Cf
CVs and resonance frequency changes as a function of poten-
tial for polymerization of FPhTT and FPhDTT were given in Fig. 8.
The frequency change was observed not to be regular in the case
of FPhTT, except for the first few cycles (Fig. 8a). This might
be explained with the formation of soluble oligomeric species of
FPhTT. The total current was not used for the polymer film for-
mation, which was considered to be consumed in the formation of
oligomers or any side products [46]. Thus, the thin film behavior
of P[FPhTT] in CV measurements could be attributed to this result.
On the other hand, a regular decrease in frequency was observed
due to the regular polymer deposition on the quartz electrode sur-
face during the polymerization of FPhDTT (Fig. 8b).
The charges, 1.65 mC and 3.5 mC, corresponding to the oxida-
tions of 8.5 × 10−9 and 1.8 × 10−8 moles of FPhTT and FPhDTT,
respectively, in the initial stage seem to be reasonable values for
the adsorbed layers of the monomers [46]. The total charges of
polymerization and the corresponding film thicknesses were 0.016
C and 418 nm for FPhTT and P[FPhTT], 0.03 C and 1170 nm for
FPhDTT and P[FPhDTT], respectively, for which the current effi-
ciency was 100%, density of the polymers was 1.4 g cm−3 , the elec-
trons used for monomer unit were 2 and the electrode surface was
0.361 cm2 .
m/Q ratio was calculated by considering the slopes of linear
part of Q - f graphs (Fig. S12) and applied for calculation of
experimental molecular weights (M) using the Eq. below:
m
M = nF (5)
Q
The current efficiencies found from the ratio of experimental
and theoretical molecular weights were 47% and 78% for P[FPhTT]
for P[FPhDTT] films. Thus, the actual thicknesses were found to
be 197 nm and 915 nm for (P[FPhTT]) and (P[FPhDTT) respec-
tively. These values were supported by the thicknesses (170 nm
and 900 nm, respectively) obtained from the measurements by us-
ing KLA Tencor Profiler V7.35 profilometer. According to these re-
sults, P[FPhDTT] film was about 5 times thicker than P[FPhTT].
Although there was some difference in the ratio obtained from
EQCM and CV methods (calculated by Eq. 1), due to the doping de-
S. Topal, S. Topal, P. Ulukan et al.
Fig. 8. CVs and resonance frequency changes as a function of potential for polymerization of FPhTT (a) and FPhDTT (b) in 1 mM monomer solution in 0.1 M Bu4 NPF6 /ACN
at 100 mV/s.
Fig. 9. CVs and resonance frequency changes as a function of potential for P[FPhTT] (a) and P[FPhDTT] (b) in 0.1 M Bu4 NPF6 containing ACN.
gree, density, differences of the electrodes (gold and GC) and cur-
rent efficiency, both methods showed that a thicker film formed
for P[FPhDTT]. This result explains the difference in the redox be-
havior of the polymers.
Since the quartz resonance frequency changes by masses of the
polymers due to doping/dedoping prosesses [47–51], charge com-
pensations of P[FPhTT] and P[FPhDTT] films, caused by their up-
take/release capabilities, were investigated by using EQCM tech-
nique combined with CV in 0.1 M TBAPF6 /ACN (Fig. 9). The EQCM
studies of P[FPhTT] and P[FPhDTT] films suggested that PF6 −
probably moves into the polymer chains.
CV and QCM graphs (Fig. 9) were divided into three potential
areas to investigate charging and discharging cycles. There were
no changes in the resonance frequency and the current density
in the potential range of 0.0-0.4 and 0.0-0.8 V for P[FPhTT] and
P[FPhDTT], respectively, implying no significant PF6 − anion dop-
ing or de-doping. In the following potential windows from 0.5 V to
1.5 V for P[FPhTT] and from 1.1 to 1.4 V for P[FPhDTT], the poly-
mers showed oxidation peaks and the frequency changes reaching
maxima, indicating the generation of positive charges in the poly-
mer backbones. However, they did not yet showed anion doping
as oxidation led to the contraction. In the last oxidation poten-
tial windows (1.5 V to 1.7 V for P[FPhTT] and 1.4 V to 1.6 V for
P[FPhDTT]), with a further oxidation of the polymers, current in-
tensities increased and the resonance frequency decreased signifi-
cantly, which was a clear indication of PF6 − anion doping.
2.6. Galvanostatic charge-discharge
Charging and discharging behaviors of P[FPhTT] and P[FPhDTT]
films were investigated by obtaining GCD curves at different cur-
rent densities in ACN containing 0.1 M Bu4 NPF6 electrolyte us-
ing three electrodes cell configuration (Fig. 10). When GCD curves
were obtained by applying the current densities in the range of
1.25 A/g to 15 A/g, the films exhibited symmetrical and deviated
triangles due to pseudocapacitive behavior of the polymers, indi-
6
Electrochimica Acta 390 (2021) 138837
cating a reversible charging and discharging conditions. P[FPhDTT]
exhibited longer discharge time as compared to P[FPhTT].
In GCD curves, linear regions (capacitive) between 0.0 V-0.6 V
and 0.0-0.9 V, and nonlinear regions (Faradic) between 0.6 V-1.5 V
and 0.9 V-1.5 V for P[FPhTT] and P[FPhDTT], respectively, were
observed as reported for similar CPs [52]. Charge and discharge
graphs were in agreement with the current increases in the CVs
of P[FPhTT] and P[FPhDTT] films and with the frequency changes
in EQCM in the same potential ranges (Fig. 2 and Fig. 9).
Energy (ED) and power densities (PD) were calculated using the
GCD curves at different current densities, using the following Eqs.
(6,7);
V ·t ·I
EQ = (6)
3600.2.m
ED
PD = (7)
t
Where V is the cut off voltage, t is the discharge time, I is the
current, m is the active masses of P[FPhTT] and P[FPhDTT] films
and results were summarized in Table 2.
The capacitances(CGCD ) were also calculated from GCD curves
by using Eq. 8 and given in Table 2. P[FPhDTT] had higher ED and
CGCD as compared to P[FPhTT], which might be due to the more
regular deposition of P[FPhDTT] film at the same polymerization
charge and conditions.
2ED
CGCD = (8)
V 2
2.7. Spectroelectrochemistry
For spectroelectrochemical measurements, FPhTT and FPhDTT
were electrodeposited on ITO working electrodes as mentioned
in the polymerization procedure. Platinum and silver wires were
used as counter and pseudo-reference electrodes, respectively.
Electrochromic properties of P[FPhTT] and P[FPhDTT] films were
S. Topal, S. Topal, P. Ulukan et al. Electrochimica Acta 390 (2021) 138837

Fig. 10. GCD curves of P[FPhTT] (a) and P[FPhDTT] (b) at different current densities.

Table 2
PD, ED and CGCD values of the polymers.

Polymers Current Density (A/g) 1.5 3 6 9 12 15

P[FPhTT] PD (W/kg) 784 1595 3229 4862 6721 8336

ED (Wh/kg) 2.99 2.71 2.39 2.16 1.74 1.55
CGCD, (mF/g) 2661 2410 2129 1921 1543 1379
Current Density (A/g) 1.25 2.5 5 7.5 10 12.5
P[FPhDTT] PD (W/kg) 665 1337 2646 3922 5185 6527
ED (Wh/kg) 4.25 4.77 3.24 2.83 2.45 2.14
CGCD, (mF/g) 3784 4240 2881 2518 2177 1902

Fig. 11. UV-visible absorption spectra of P[FPhTT] (a) and P[FPhDTT] (b) on ITO electrodes at different applied potentials.

Table 3
Optical band gap of FPhTT, FPhDTT and their non-fluorine analogues.

Monomer Polymer
λmax (nm) λonset (nm) Eg (eV) λmax (nm) λonset (nm) Eg (eV)

FPhTT 257/282 315 3.93 450 760 1.63

FPhDTT 263 333 3.72 460 698 1.77
PhTT [12] 300 329 3.75 328/460 600 2.05
PhDTT [53,54] 260/293 331 3.74 422 568 2.18

monitored by electrochemical and UV-visible spectrophotometric
measurements at different potentials. Band gaps of the monomers
and the polymers were obtained from their onset absorptions (Fig.
S6 and Fig. 11, respectively, Table 3). As it be seen the band gap of
P[FPhTT] and P[FPhDTT] were found lower than their correspond-
ing monomers as well as their non-fluorinated analogues. Regard-
ing P[FPhTT], a decrease in the absorbance at 450 nm, which is
due to the π -π ∗ transition band, and a new peak at 665 nm with
an increase in anodic potential were observed with an isobestic
point at 600 nm due to the formation of polarons on the P[FPhTT]
chain. Further oxidation beyond 1.7 V resulted in a new broad band
at 1060 nm due to the formation of bipolarons. These changes, ob-
served in the UV-visible spectra, were supported with the change
in colors of P[FPhTT] film from orange (at 0.0 V) to green and blue
(at 1.0 and 1.5 V), respectively.
Regarding P[FPhDTT], with the increase in the applied poten-
tial, the absorption band at 460 nm decreased and a new band
was detected at 765 nm with an isobestic point at 650 nm due to
the oxidation and formation of polarons (Fig. 11b). As the oxida-
tion was continued a new broad peak appeared at 1055 nm due
to the bipolaron formation. The color of P[FPhDTT] film changed
from brown in neutral state (at 0.0 V) to green and blue in its ox-
idized states (at 1.1 and 1.4 V, respectively) (Fig. 12).
Optoelectrochemical stability is one of the most important pa-
rameter for electrochromic materials and completely different from
electrochemical stability as it could be lost even if the electroactiv-
ity of a polymer is preserved [55]. Considering this approach, opti-
cal contrast changes of P[FPhTT] was investigated at 450, 665 and
1060 nm, while switching between 0.0 V and 1.5 V, with a resi-
dence time of 10 s (Fig. 13a). For the P[FPhDTT], the same mea-

7
S. Topal, S. Topal, P. Ulukan et al. Electrochimica Acta 390 (2021) 138837

Fig. 12. Electrochromic behavior of P[FPhTT] (a) and P[FPhDTT] (b) film on electrolyte solution.

Fig. 13. Optical contrasts of P[FPhTT] (a) and P[FPhDTT] (b) films.

Fig. 14. AFM images and topography plots of P[FPhTT] (a) and P[FPhDTT] (b).

surement was performed at 460 nm with potentials between 0.0
and 1.5 V at the same residence time (Fig. 13b). P[FPhTT] exhib-
ited a stable optoelectrochemical behavior, unlike P[FPhDTT]. Op-
tical contrasts of P[FPhTT] at 450, 665 and 1060 nm were found
to be 14%, 8% and 12%, respectively (Fig. 13).
Coloration efficiency (CE) is defined as power efficiency to
change color of an electrochromic material, which is calculated by
optical density using the Eq. below;
OD
CE =
Qd
Where the Qd is the injected-ejected charge during the redox pro-
cess; OD=log (Tcolored /Tbleached ), Tcolored and Tbleached are the
transmittance at the oxidized and neutral states, respectively. CE
values were found as 123 at 450 nm, 57 at 665 nm and 122 at
1060 nm.
2.8. Surface analysis
For surface analyses, P[FPhTT] and P[FPhDTT] films on ITO
(9) were prepared in the same conditions of spectroelectrochemical

8
S. Topal, S. Topal, P. Ulukan et al.
Fig. 15. Molecular Orbitals (MOs) of FPhTT (a), FPhDTT (b), DiFPhTT (c) and DiFPhDTT (d) at B3LYP/6-311G level (Isosurface value: 0.04 a.u.).
measurements. AFM images showed that P[FPhTT] had very small
beats and smoother surface compared to P[FPhDTT] (Fig. 14). Root-
mean-square (RMS) roughness values of P[FPhTT] and P[FPhDTT]
were found to be 3 and 94 nm, respectively. Surface porosity
of electrodes is a significant parameter for enhancing the en-
ergy storage capacity. The porosity increases the intercalation/de-
intercalation reactions between electrode and supporting elec-
trolyte ions [56–58]. This result supports that the higher ca-
pacitance value of P[FPhDTT] was due to its more porous
structure.
2.9. Computational studies
Geometry optimization of the monomers and dimers were per-
formed applying DFT B3LYP method and the basis set 6-311G
without any symmetry (results were verified with NImag = 0)
(Fig. 15). Spin densities of the radical cations were calculated by
B3LYP/6-311++G(d,p) with CPMC (ACN, electrochemical polymer-
ization condition) polarizable conductor model [59]. The isosurface
values of 0.04 and 0.004 a.u. were applied for visualization of MO
and spin densities, respectively, with GausView 5.0.8.
Gas phase optimizations of FPhTT and FPhDTT provided that
the phenyl groups on their structures cause deviations from the
9
Electrochimica Acta 390 (2021) 138837
planarity of TT and DTT by 40° and 41°, which rose up to 43° and
63° in dimer form, respectively. Fig. 16 shows that HOMO com-
pletely located on TT and DTT units apart from the phenyl groups.
LUMO was predicted to be spreading on whole TT and DTT groups.
Additionally, LUMOs of the dimers of FPhTT and FPhDTT were pre-
dicted to concentrate around the bonds connecting two TT and DTT
units.
Spin densities of the radical cations of FPhTT+• at α -carbons
(C4 and C7) were found to be 0.409 and 0.224, respectively
(Fig. 16a). This result indicated that α -carbons are good candidates
for electrochemical polymerization. Further computational studies
were performed for head to head dimeric form of FPhTT (DiF-
PhTT) to support the polymerization mechanism. Computational
studies predicted the spin densities of radical cations (FPhDTT+•)
on α -carbons (C7 and C10) as 0.336, suggesting the polymerization
through α -carbons (Fig. 16b).
Spin density of 0.165 on α -carbons (C7 and C32) at the periph-
erals of TT was found to be suitable for a further polymerization
(Fig. 16c).
Additionally, radical cation of dimeric form (DiFPhDTT +•) was
generated having a spin density of 0.157 on α -carbons C7 and C55
of DTTs (Fig. 16d). These densities suggested a good candidate for
the polymerization.
S. Topal, S. Topal, P. Ulukan et al.
Fig. 16. Spin densities and spin surfaces of radical cations of monomers and head to head dimers: FPhTT (a), FPhDTT (b), DiFPhTT (c) and DiFPhDTT (d) at B3LYP/6-
311++G(d,p) (CMP:DCM) level (isosurface value: 0.004, hydrogens were omitted for clarity).
3. Conclusion
In this study, FPhTT and FPhDTT were synthesized and suc-
cessfully electropolymerized and results suggested that the poly-
merization rate of FPhDTT was higher than FPhTT, possibly due
to having symmetric and more conjugated structure. Consequently,
the corresponding polymer, P[FPhDTT], had higher current density
with thicker film compared to P[FPhTT] at the same deposition
conditions.
On the other hand, electron transfer reaction rate of P[FPhTT]
was faster than the rate of P[FPhDTT]. P[FPhTT] showed reversible
redox behavior even at higher scan rates and behaved as thin film,
while P[FPhDTT] had diffusion controlled mechanism.
Electrochemical and spectroelectrochemical results suggested
that P[FPhTT] had lower oxidation potential and optical band
gap than P[FPhDTT], additionally, P[FPhTT] exhibited more sta-
ble optoelectrochemical behavior compared to P[FPhDTT]. On the
other hand comparison of the optical measurement results sug-
gested that the band gap of P[FPhTT] and P[FPhDTT] were found
10
Electrochimica Acta 390 (2021) 138837
lower than their corresponding monomers as well as their non-
fluorinated analogues obtained previously.
EQCM measurements indicated that while regular polymer-
ization was observed in the case of FPhDTT, irregular polymer-
ization was observed with FPhTT due to soluble oligomers for-
mation and/or consumption of some of the charge during side
reactions.
EIS measurements of P[FPhTT] and P[FPhDTT] films had good
agreement with their CVs and the best capacitance values were
obtained at their oxidation peak potentials, 1.0 V and 1.2 V, re-
spectively. Similar tendency was observed during the GCD and CV
measurements and supported this result.
Electropolymerization mechanism was supported by the spin
density values calculated at DFT level.
In addition, AFM images suggested that P[FPhDTT] exhibited
more porous structure than P[FPhTT], which could be a possible
proof for the higher capacitance value of P[FPhDTT].
As a conclusion, P[FPhTT] and P[FPhDTT] could be suitable al-
ternatives for energy storage and optical applications due to their
S. Topal, S. Topal, P. Ulukan et al.
high energy and power densities and multiple electrochromic be-
haviors.
Credit Author Statement
Esma Sezer: Supervision, Visualization, Original draft prepara-
tion, Investigation, Methodology, Funding Acquisition, Reviewing.
Belkıs Ustamehmetoğlu: Writing and Editing, Methodology,
Conceptualization, Reviewing.
Turan Öztürk: Original draft preparation, Methodology, Writing
and Editing, Reviewing.
Sema Topal: Synthesis, Data collection and Presentation, Writ-
ing, Investigation, Methodology.
Sebahat Topal: Synthesis, Data collection and Presentation,
Writing.
Pelin Ulukan: Synthesis and Data collection.
Declaration of Competing Interest
The author(s) declared no potential conflicts of interest with re-
spect to the research, authorship, and/or publication of this article.
Acknowledgment
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., 10 0/20 0 0 YOK) for for grants to Se-
bahat Topal. In addition, we would like to thank Istanbul Technical
University Scientific Research Projects (Project No: 42325) and Un-
sped 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.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.electacta.2021.138837.
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