molecules

Article
Experimental and Theoretical Studies on Indigo-Dye-Modified
Conjugated Polymers
Tionna Douglas 1 , Neetika Singh 2,3 and Ufana Riaz 1,2, *

1 Department of Chemistry and Biochemistry, North Carolina Central University, Durham, NC 27707, USA
2 Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025, India
3 Department of Materials Engineering, Indian Institute of Science, Bengaluru 560012, India
* Correspondence: [email protected] or [email protected]

Abstract: The present work reports the synthesis of indigo-dye-incorporated polyaniline (Indigo-
PANI), poly(1-naphthylamine) (Indigo-PNA), poly(o-phenylenediamine) (Indigo-POPD), polypyrrole
(Indigo-PPy), and polythiophene (Indigo-PTh) via an ultrasound-assisted method. The synthesized
oligomers were characterized using FTIR, UV–visible spectroscopy, X-ray diffraction (XRD), scan-
ning electron microscopy (SEM), fluorescence studies, and thermogravimetric analysis (TGA). The
experimental data were theoretically compared to analyze the vibrational and electronic spectra
via time-dependent density-functional theory (TD-DFT) by applying the Becke, three-parameter,
and Lee-Yang-Parr (B3LYP) method with a 6-311G (d,p) basis set. The experimental, theoretical
vibrational, and electronic spectra were found to be in close agreement and confirmed the successful
incorporation of indigo dye in PANI, PNA, POPD, PPy, and PTh. These studies confirmed that multi-
functional oligomers could be synthesized through a facile technique by incorporating dye moieties
to enhance their optoelectronic properties, allowing them to be utilized as near-infrared-emitting
probes for photodynamic therapy.

Keywords: indigo; conducting polymer; theoretical studies; UV–visible; fluorescence

Citation: Douglas, T.; Singh, N.; Riaz, 1. Introduction

U. Experimental and Theoretical
Conjugated polymers such as polyaniline (PANI) [1], polycarbazole (PCz) [2], polythio-
Studies on Indigo-Dye-Modified
phene (PTh) [3], polypyrrole (PPy) [4], poly(1-naphthylamine) (PNA) [5], poly(o-phenylene-
Conjugated Polymers. Molecules 2024,
diamine) (POPD) [6], etc., have received considerable attention as organic electrochromic mate-
29, 3200. https://doi.org/10.3390/
rials due to their outstanding photo-physical and optoelectronic properties [7]. Several poly-
molecules29133200
merization techniques, such as copolymerization [8], grafting [9], and functionalization [10,11],
Academic Editors: Cuiying Jian have been employed to enhance the extent of conjugation in these polymers, a factor responsible
and Aleksander Czekanski for their remarkable electronic and conductivity characteristics.
Received: 23 May 2024
Among these methods, dye incorporation is regarded as one of the most facile methods
Revised: 25 June 2024
of enhancing the functionality and extent of conjugation for designing polymers with im-
Accepted: 25 June 2024 proved optoelectronic properties. The doping of POPD with dyes such as Acid Orange (AO),
Published: 5 July 2024 Fluorescein (Fluo), and Rhodamine-6G (R6G) to design photosensitive and fluorescent poly-
mers has been reported [12]. Similarly, the modification of PANI and POPD with Sudan-I
dye has also been carried out via a microwave-assisted method [13]. The quantum yield (Φ)
values were calculated to be 0.40 and 0.54 for dye-modified PANI and POPD, respectively.
Copyright: © 2024 by the authors. Ultrasound-assisted polymerization of azobenzene with aniline, 1-naphthylamine, luminol,
Licensee MDPI, Basel, Switzerland. and o-phenylenediamine also led to enhanced photo-physical characteristics [14].
This article is an open access article Recently, the oligomerization of Bismarck Brown (BB) dye was attempted with luminol,
distributed under the terms and and success was confirmed via experimental as well as theoretical IR and UV-visible
conditions of the Creative Commons
studies [15]. The highest occupied molecular orbital (HOMO) and lowest unoccupied
Attribution (CC BY) license (https://
molecular orbital (LUMO) energies showed a significant reduction in the band gap upon
creativecommons.org/licenses/by/
increasing the content of BB dye.
4.0/).

Molecules 2024, 29, 3200. https://doi.org/10.3390/molecules29133200 https://www.mdpi.com/journal/molecules

 nol, and success was confirmed via experimental as well as theoretical IR and UV-visible
studies [15]. The highest occupied molecular orbital (HOMO) and lowest unoccupied mo-
lecular orbital (LUMO) energies showed a significant reduction in the band gap upon in-
creasing the content of BB dye.
Indigo and its derivatives have long been used for their intense color and high pho-
Molecules 2024, 29, 3200 2 of 15
tochemical stability [16,17]. Electronic materials derived from indolo-naphthyridine have
been investigated for their optoelectronics properties, while isoindigo-based conjugated
polymers have been designed for the development of semiconducting materials [18–20]
Indigo and its derivatives have long been used for their intense color and high pho-
Indigo-based
tochemical polymers
stability [16,17].containing thermo-cleavable
Electronic materials derived from -butoxycarbonyl (t-Boc)
tertindolo-naphthyridine have groups
have shown electron mobility of ∼6 × 10 −3 cm2 V−1 s−1, which is an almost 5-fold increase
been investigated for their optoelectronics properties, while isoindigo-based conjugated
comparedhave
polymers to that
beenofdesigned
indigo-based
for thepolymers
development alone due to high backbone
of semiconducting materialscoplanarity
[18–20]. [20].
Few studies
Indigo-based are available
polymers containingon the modification
thermo-cleavable tert-butoxycarbonyl
of polymers/oligomers using dyes to
(t-Boc) groups
have shown electron mobility of ~6 × 10 −3 cm2 V−1 s−1 , which is an almost 5-fold increase
enhance their optoelectronic properties. Moreover, facile techniques for designing poly-
compared to that of
mers/oligomers indigo-based
with controlledpolymers
emission alone
anddue to high backbone
enhanced coplanarity
optoelectronic [20].
characteristics are
Few studies are available on the modification of polymers/oligomers using dyes to
highly desirable but have not yet been reported. Hence, with a view to study the effect of
enhance their optoelectronic properties. Moreover, facile techniques for designing poly-
indigo dye incorporation on the physico-chemical and optoelectronic properties of syn-
mers/oligomers with controlled emission and enhanced optoelectronic characteristics are
thesized
highly conjugated
desirable but havepolymers, the present
not yet been reported. study
Hence,reports
with athe synthesis
view to studyoftheindigo-dye-in-
effect
corporated
of indigo dye PANI, PNA, PPy,
incorporation on and PTh and POPD via
the physico-chemical andan ultrasound-assisted
optoelectronic propertiespolymeriza-
of
tion technique.
synthesized The chemical
conjugated polymers,structures of the
the present prepared
study reports oligomeric
the synthesisdyes were determined
of indigo-dye-
via FTIR studies,
incorporated and the
PANI, PNA, PPy,electronic
and PTh and transitions
POPD viaof anpolymeric dyes were
ultrasound-assisted determined via
polymeriza-
tion technique.
UV-vis studiesThe
and chemical structures
fluorescence of the prepared
measurements. Theoligomeric dyes were
morphologies determined
of the polymers were
via FTIR studies, and the electronic transitions of polymeric dyes were
confirmed via XRD and SEM analysis. DFT studies were carried out using the DFT/B3LYPdetermined via
UV-vis studies and fluorescence measurements. The morphologies of the polymers were
method with the 6-311 G (d,p) basis set to compare the experimental data.
confirmed via XRD and SEM analysis. DFT studies were carried out using the DFT/B3LYP
method with the 6-311G (d,p) basis set to compare the experimental data.
2. Results and Discussion
2. Results and Discussion
The viscosity average molecular weight of the polymers was determined as per the
The viscosity
method reportedaverage molecular
in our earlier weight
studies of the
[10]. Thepolymers
viscositywas determined
average as perweight
molecular the was
method reported
determined to bein4568
our earlier studies [10]. 4872
for Indigo-PANI, The viscosity average molecular
for Indigo-PNA, weight was
5223 for Indigo-POPD, 4876
determined to beand
for Indigo-PPy, 45684321
for Indigo-PANI,
for Indigo-PTh.4872Theforproposed
Indigo-PNA, 5223 for
chemical Indigo-POPD,
structures are shown in
4876 for Indigo-PPy, and 4321 for Indigo-PTh. The proposed chemical structures are
Scheme 1a-e. This scheme reveals that indigo has been incorporated as a dimer due to its
shown in Scheme 1a–e. This scheme reveals that indigo has been incorporated as a dimer
greater reactivity with itself than with the monomers. The proposed chemical structures
due to its greater reactivity with itself than with the monomers. The proposed chemical
were usedwere
structures for theoretically computing
used for theoretically the vibrational
computing and electronic
the vibrational spectra,
and electronic which were
spectra,
which were found to be in good agreement with the experimental results. Hence, the mech-
found to be in good agreement with the experimental results. Hence, the proposed
anism of mechanism
proposed the insertion of insertion
of the Indigo was acceptable
of Indigo and quite
was acceptable andsimilar to that
quite similar of other
to that of dye-
incorporated
other oligomers
dye-incorporated shown shown
oligomers in our in
previous studies
our previous [13–16].
studies [13–16].

Scheme 1. Cont.
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Scheme 1. Cont.
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Scheme1.1.Mechanism
Scheme Mechanismofofpolymerization of of
polymerization (a)(a)
Indigo-PANI, (b) Indigo-PNA,
Indigo-PANI, (c) Indigo-POPD,
(b) Indigo-PNA, (c) Indigo-POPD, (d
(d) Indigo-PPy,and
Indigo-PPy, and(e)
(e)Indigo-PTh.
Indigo-PTh.

2.1. Morphological Studies via XRD and SEM Analysis

2.1. Morphological Studies via XRD and SEM Analysis
XRD was used to explore the crystallinity of synthesized oligomers. The XRD profile
XRD
of Indigo was
dye, usedintoFigure
shown explore the crystallinity
1, revealed peaks at 2θof= synthesized
22.71◦ , 23.93◦ oligomers.
and 26.34◦ . TheTheXRDXRD profile
of Indigo
profile dye, shown
of Indigo-PANI in Figure
revealed 1, revealed
additional peaks peaks
at 2θ = at
10.61 ◦
2θ ,=14.59 ◦
22.71°, ◦
23.93°
, 19.26 , andand
31.79 ◦,
26.34°. The
besides the peaks correspondingrevealed
to the presence of Indigo dye ◦ ◦
XRD profile of Indigo-PANI additional peaks atat2θ2θ == 10.61°,
22.71 , 23.93 , and
14.59°, 19.26°, and
26.34 ◦ . The new peaks were correlated with the planes associated with PANI, while the
31.79°, besides the peaks corresponding to the presence of Indigo dye at 2θ = 22.71°
peaks
23.93°, corresponding
and 26.34°. The to Indigo
new dye
peaks revealed
were the same intensity
correlated with the as that in the
planes pristine XRD
associated with PANI
profile of the dye, which confirmed that no major structural reorganization occurred upon
while the peaks corresponding to Indigo dye revealed the same intensity as that in the
the incorporation of Indigo dye in PANI. The XRD profile of Indigo-PNA displayed peaks
pristine XRD profile of the dye, which confirmed that no major structural reorganization
at 2θ = 10.76◦ , 14.54◦ , 18.23◦ , 22.71◦ , 23.76◦ , 26.50◦ , and 31.63◦ . The polymer revealed semi-
occurred upon the incorporation of Indigo dye in PANI. The XRD profile of Indigo-PNA
displayed peaks at 2θ = 10.76°, 14.54°, 18.23°, 22.71°, 23.76°, 26.50°, and 31.63°. The poly
mer revealed semi-crystallinity like that noticed in Indigo-PANI. The XRD profile of In
digo-POPD exhibited peaks ranging from 2θ = 10.47 to 31.93°, while Indigo-PPy revealed
 Molecules 2024, 29, 3200 5 of 15
Molecules 2024, 29, x FOR PEER REVIEW 5 of 16

crystallinity like that noticed in Indigo-PANI. The XRD profile of Indigo-POPD exhibited
peaks ranging from 2θ = 10.47 to 31.93◦ , while Indigo-PPy revealed peaks ranging from
peaks in the
2θ = 10.76 ◦ tosame
31.17◦range. Theprofile
. The XRD incorporation of Indigo
of Indigo-PTh in PANI,
also revealed PNA,
peaks POPD,
in the samePPy, and PTh
range.
led to a minor shifting of peaks, and the appearance of new sharp
The incorporation of Indigo in PANI, PNA, POPD, PPy, and PTh led to a minor shiftingpeaks confirmed the
presence of well-formed
of peaks, and the appearanceplanes
of newin sharp
the polymers [13]. Thethe
peaks confirmed incorporation of Indigo contrib-
presence of well-formed
uted
planestoincrystallinity
the polymers and did
[13]. not
The result in anyofstructural
incorporation reorganization
Indigo contributed for anyand
to crystallinity of the dye-
did not result
modified in any structural
polymers [12,13]. reorganization for any of the dye-modified polymers [12,13].

Figure 1. XRD data for Indigo-PANI, Indigo-PNA, Indigo-POPD, Indigo-PPy, and Indigo-PTh.
Figure 1. XRD data for Indigo-PANI, Indigo-PNA, Indigo-POPD, Indigo-PPy, and Indigo-PTh.
The SEM data for Indigo-PANI (Figure 2a) show the formation of a two-dimensional
(2D) The
jagged
SEMsheet-like structure,
data for while the
Indigo-PANI SEM data
(Figure for Indigo-PNA,
2a) show shown
the formation of in Figure 2b,
a two-dimensional
reveal a granular aggregated morphology of variable sizes. The SEM results for Indigo-
(2D) jagged sheet-like structure, while the SEM data for Indigo-PNA, shown in Figure 2b,
POPD, shown in Figure 2c, and Indigo-PPy, shown in Figure 2d, exhibit a flaky structure
reveal a granular aggregated morphology of variable sizes. The SEM results for Indigo-
with highly stacked clusters. The SEM results for Indigo-PTh, shown in Figure 2e, re-
POPD,
veal theshown in Figure
formation 2c, androds
of elongated Indigo-PPy,
mixed with shown in Figure 2d, exhibit
flaky agglomerates. a flaky structure
The morphology
with highly
appeared stacked
to be clusters.
crystalline in allThe SEM
cases, andresults forwas
this fact Indigo-PTh, shown in
also corroborated byFigure
the XRD 2e, reveal
the formation
results. of elongated
The morphology was rods
foundmixed
to varywith flaky
for all agglomerates.
the oligomers, The morphology
confirming that the ap-
type of monomer into which Indigo was incorporated governed the morphology
peared to be crystalline in all cases, and this fact was also corroborated by the XRD results. in all
cases.
The Indigo-PPy showed
morphology was found different huge
to vary forflaky structures.
all the oligomers, Indigo-PTh showed
confirming distorted,
that the type of mon-
rod-like structures embedded within it along with a granular morphology.
omer into which Indigo was incorporated governed the morphology in all cases. Hence, it can Indigo-
be concluded that the selection of the appropriate monomer could be used to control the
PPy showed different huge flaky structures. Indigo-PTh showed distorted, rod-like struc-
architecture of the oligomers.
tures embedded within it along with a granular morphology. Hence, it can be concluded
that the selection of the appropriate monomer could be used to control the architecture of
the oligomers.
Molecules 2024, 29, 3200 6 of 15
Molecules 2024, 29, x FOR PEER REVIEW 6 of 16

Figure 2.
Figure 2. SEM
SEMimages ofof
images (a)(a)
Indigo-PANI, (b) Indigo-PNA,
Indigo-PANI, (c) Indigo-POPD,
(b) Indigo-PNA, (d) Indigo-PPy,
(c) Indigo-POPD, and
(d) Indigo-PPy, and
(e) Indigo-PTh.
(e) Indigo-PTh.
2.2. Thermogravimetric
2.2. Thermogravimetric Analysis
Analysis
The TGA
The TGA profiles
profilesofofIndigo
Indigodye,
dye,Indigo-PANI, Indigo-PNA,
Indigo-PANI, Indigo-POPD,
Indigo-PNA, Indigo-POPD,Indigo-
Indigo-PPy,
PPy, and Indigo-PTh are depicted in Figure 3a–e. The TGA profile of pure indigo dye,
and Indigo-PTh are depicted in Figure 3a–e. The TGA profile of pure indigo dye, shown in
shown in Figure 3a, revealed 5 wt.% loss around 100 ℃ and 20 wt.% loss at 400 ℃ corre-
Figure 3a, revealed 5 wt.% loss around 100 °C and 20 wt.% loss at 400 °C corresponding to
sponding to the decomposition of the carbonyl group.
the decomposition of the carbonyl group.
The DTG profiles showed a broad exotherm around 100 ◦ C and a sharp endotherm
at 400 ◦ C, results correlated with the decomposition of the dye molecule through the frag-
mentation of carbonyl groups. Around 35 wt.% loss was noticed at 500 ◦ C, while 70 wt.%
decomposition was noticed at 800 ◦ C. The TGA profile of Indigo-PANI, shown in Figure 3b,
also revealed almost 2 wt.% loss around 100 ◦ C due to evaporation of moisture, whereas
10 wt.% loss was noticed around 298 ◦ C, and the DTG showed a sharp exothermic event,
which was correlated with structural reorganization of the polymer prior to decomposition.
Almost 30 wt.% loss was achieved at 500 ◦ C, and 55 wt.% loss was observed at 800 ◦ C,
confirming the polymer to be thermally stable. Likewise, The TGA profile of Indigo-PNA
(Figure 3c) showed the occurrence of multiple exothermic events prior to 400 ◦ C, and a
broad exotherm was noticed around this temperature, showing almost 20 wt.% degrada-
tion. The presence of multiple exotherms spanning between 150 ◦ C and 350 ◦ C could be
correlated with structural reorganization of the oligomeric chains prior to decomposition,
and almost 68 wt.% loss was noticed at 800 ◦ C. The polymer was found to be less stable
than Indigo-PANI. The TGA profile of Indigo-POPD (Figure 3d) showed 25 wt. % loss
at 350 ◦ C and a sharp exothermic event around this temperature. The maximum loss of
45 wt.% was noticed at 800 ◦ C, and the polymer showed higher thermal stability than
Indigo-PNA and Indigo-PANI. Interestingly, the TGA profiles of Indigo-PPy, shown in
Figure 3e, exhibit a sharp and pronounced exothermic event at 375 ◦ C corresponding to
Molecules 2024, 29, 3200 7 of 15

40 wt.% loss of the polymer due to the decomposition of the dye moiety as well as the
heterocyclic rings, while 60 wt.% decomposition took place at 800 ◦ C. The TGA profile
of Indigo-PTh, shown in Figure 3f, reveals multiple exothermic events spanning from
100 to 200 ◦ C, 200 to 300 ◦ C, 400 to 500 ◦ C, and 600 to 700 ◦ C, confirming that the polymer
had a highly branched structure, which presumably caused rapid structural reorganization
at every decomposition temperature. Almost 20 wt.% decomposition was seen at 350 ◦ C,
while 45 wt.% decomposition took place at 800 ◦ C. The TGA-DTG profiles7clearly
Molecules 2024, 29, x FOR PEER REVIEW of 16 revealed

that the polymers were highly stable.

.
Figure 3. TGA-DTG profiles of (a) pure indigo dye, (b) Indigo-PANI, (c) Indigo-PNA, (d) Indigo-
Figure 3. TGA-DTG profiles of (a) pure indigo dye, (b)Indigo-PANI, (c) Indigo-PNA, (d) Indigo-
POPD, (e) Indigo-PPy, and (f) Indigo-PTh.
POPD, (e) Indigo-PPy, and (f) Indigo-PTh.
2.3. Fluorescence Studies
The DTG profiles showed a broad exotherm around 100 °C and a sharp endotherm
The
at 400 °C, fluorescence
results correlatedemission spectra of theofIndigo-dye-modified
with the decomposition the dye molecule through polymers
the frag- (excited at
380 nm)ofare
mentation depicted
carbonyl in Figure
groups. Around4.35 Thewt.%emission spectrum
loss was noticed of°CIndigo-PANI
at 500 , while 70 wt.% revealed an
intense peakwas
decomposition at 500 nm,atwhile
noticed theThe
800 °C. emission spectra
TGA profile of Indigo-PNA
of Indigo-PANI, also
shown inexhibited
Figure intense
3b,emission at 510almost
also revealed nm upon
2 wt.%excitation
loss aroundat 380
100nm. The to
°C due emission spectrum
evaporation of Indigo-POPD
of moisture,
showed
whereas a broad
10 wt.% losspeak at 550 around
was noticed nm, and 298the
°C,emission
and the DTGspectra
showedof Indigo-PPy and Indigo-PTh
a sharp exothermic
event, whichpeaks
revealed was correlated
at 480 nmwith
andstructural reorganizationThe
600 nm, respectively. of the polymeryields
quantum prior to
(Φ)decom-
of the oligomers
position. Almost 30as
were calculated wt.%
perloss
the was achieved
reported at 500using
method, °C, and 55 wt.% loss
Rhodamine was
B as observed at
a reference [15–18]. The
800Φ°C, confirming
values obtainedthe were
polymer
3.2 to
× be10−thermally
4 , 6.2 × 10stable. Likewise,
−3 , 5.3 × 10−3The, 4.0TGA
× 10profile
−4 , andof 1.6
In- × 10−3 for
digo-PNA (FigureIndigo-PNA,
Indigo-PANI, 3c) showed the occurrence of multiple
Indigo-POPD, exothermic
Indigo-PPy, events priorrespectively.
and Indigo-PTh, to 400 The
°C, and a broad exotherm was noticed around this temperature, showing almost 20 wt.%
highest quantum yield was observed for Indigo-PNA, while the lowest quantum yield
degradation. The presence of multiple exotherms spanning between 150 °C and 350 °C
was noticed in the case of Indigo-PPy, as shown in Table 1. This could be attributed to the
could be correlated with structural reorganization of the oligomeric chains prior to de-
composition, and almost 68 wt.% loss was noticed at 800 °C. The polymer was found to be
less stable than Indigo-PANI. The TGA profile of Indigo-POPD (Figure 3d) showed 25 wt.
% loss at 350 °C and a sharp exothermic event around this temperature. The maximum
loss of 45 wt.% was noticed at 800 °C, and the polymer showed higher thermal stability
than Indigo-PNA and Indigo-PANI. Interestingly, the TGA profiles of Indigo-PPy, shown
 showed a broad peak at 550 nm, and the emission spectra of Indigo-PPy and Indigo-PTh
revealed peaks at 480 nm and 600 nm, respectively. The quantum yields (Ф) of the oligo-
mers were calculated as per the reported method, using Rhodamine B as a reference [15–
18]. The Ф values obtained were 3.2 × 10−4, 6.2 × 10−3, 5.3 × 10−3, 4.0 × 10−4, and 1.6 × 10−3 for
Indigo-PANI, Indigo-PNA, Indigo-POPD, Indigo-PPy, and Indigo-PTh, respectively. The
Molecules 2024, 29, 3200 8 of 15
highest quantum yield was observed for Indigo-PNA, while the lowest quantum yield
was noticed in the case of Indigo-PPy, as shown in Table 1. This could be attributed to the
structural orientation and twisting of the oligomeric chains upon the insertion of Indigo
dye, which lowered
structural the quantum
orientation yield values.
and twisting of the oligomeric chains upon the insertion of Indigo
dye, which lowered the quantum yield values.

Figure 4. Fluorescence emission spectra of Indigo-PANI, Indigo-PNA, Indigo-POPD, Indigo-PPy, and

Figure 4. Fluorescence emission spectra of Indigo-PANI, Indigo-PNA, Indigo-POPD, Indigo-PPy,
Indigo-PTh.
and Indigo-PTh.
Table 1. Fluorescence quantum yields of Indigo-PANI, Indigo-PNA, Indigo-POPD, Indigo-PPy, and
Table 1. Fluorescence quantum yields of Indigo-PANI, Indigo-PNA, Indigo-POPD, Indigo-PPy, and
Indigo-PTh.
Indigo-PTh.

Polymers
PolymersPeak Position (nm)
Peak Position (nm) Area Area Quantum yield
Quantum Yield
Indigo-PANI 500 8.8 × 104 3.2 × 10−4
Indigo-PANI 500 8.8 × 104 3.2 × 10−4
Indigo-PNA 510 2.2 × 106 6.2 × 10−3
2.2 × 106 −3
Indigo-PNA
Indigo-POPD 550 510 4.6 × 106 5.3 × 10−3 6.2 × 10
Indigo-PPy
Indigo-POPD 480 550 1.8 × 105 4.6 × 106 4.0 × 10−4 5.3 × 10−3

Indigo-PPy 480 1.8 × 105 4.0 × 10−4

Indigo-PTh 650 8.0 × 104 1.6 × 10−3

2.4. Comaprison of Experimental Data with Computational Studies to Confirm the Proposed
Structures of Indigo-Dye-Modified Oligomers Using DFT: Optimized Geometries and Frontier
Molecular Orbitals
The Indigo-dye-modified oligomers were optimized by inserting one monomeric unit
of dye and two units of monomer flanked on either side of the dye molecule, as shown
in Figure 5a–e. The optimized geometry of Indigo-PANI, depicted in Figure 5a, showed
a planar configuration. The optimized geometry of Indigo-PNA, shown in Figure 5b,
exhibited a twisted configuration. The optimized geometries of Indigo-POPD, Indigo-PPy,
and Indigo-PTh, shown in Figure 5c–e, also revealed a planar configuration with no visible
twisting upon insertion of the Indigo dimer.
The Muliken charge distribution for Indigo-PANI, Indigo-PNA, and Indigo-POPD
(given in Figure S1a–c in the Supporting Information) was found to be centered around
the N atoms of the amide NH- group as well as on the C=O groups of the Indigo dye. For
Indigo-PPy, shown in Figure S1d, the charge was found to be concentrated around the NH
of PPy and the C=O groups of the Indigo dye, while for Indigo-PTh, shown in Figure S1e,
it was noticed to be centered around the C=O groups of Indigo and also around the C–C
bonds linked to the S group.
The frontier molecular orbitals were computed to explore the changes in the bandgap
upon insertion of Indigo dimer in the oligomers. The highest occupied molecular orbital
(HOMO) of Indigo-PANI, shown in Figure 6a, was found to be evenly distributed over
the backbone of the dye moiety, while the lowest unoccupied molecular orbital (LUMO)
appeared to be less symmetric and completely distributed along the aniline ring. The
HOMO-LUMO energy was computed to be 1.25 eV. For Indigo-PNA, shown in Figure 6b,
 Molecules 2024, 29, x FOR PEER REVIEW 9 of 16
Molecules 2024, 29, 3200 9 of 15

Indigo-PTh 650 8.0 × 104 1.6 × 10−3

the LUMO orbitals were noticed to be concentrated around C–C linkage of Indigo dye, and
2.4. 1-napththylamine
the Comaprison of Experimental Data with
monomer Computational
ring and the HOMOStudies to Confirmwere
orbitals the Proposed
uniformly distributed
over the Indigo dimer. The HOMO-LUMO energy was determinedand
Structures of Indigo-Dye-Modified Oligomers Using DFT: Optimized Geometries toFrontier
be 1.17 eV and lower
Molecular Orbitals
than that of Indigo-PANI due to the presence of a fused benzene ring, which increased the
The Indigo-dye-modified oligomers were optimized by inserting one monomeric
extent of conjugation in the oligomer. The oligomer Indigo-POPD, depicted in Figure 6c,
unit of dye and two units of monomer flanked on either side of the dye molecule, as shown
showed symmetrically distributed HOMO/LUMO orbitals, and the energy was computed
in Figure 5a–e. The optimized geometry of Indigo-PANI, depicted in Figure 5a, showed a
to be 1.04
planar eV. Likewise,
configuration. for Indigo-PPy
The optimized geometryand Indigo-PTh,
of Indigo-PNA, shown
shown in Figure
in Figure 6d,e, the HOMO-
5b, exhib-
LUMO distribution
ited a twisted was quite
configuration. symmetrical
The optimized and concentrated
geometries of Indigo-POPD, around the linkage
Indigo-PPy, and connecting
the dye andshown
Indigo-PTh, the monomer molecule.
in Figure 5c–e, The HOMO-LUMO
also revealed energies
a planar configuration with were computed to be
no visible
twisting
1.18 eV upon
and 1.08insertion of the
eV for Indigo dimer.
Indigo-PPy and Indigo-PTh, respectively. The incorporation of
Indigo Thewas
Muliken
found charge distribution
to result for Indigo-PANI,
in variable HOMO-LUMO Indigo-PNA,
energy and Indigo-POPD
values, which were found to
(given in Figure S1a–c in the Supporting Information) was found to be centered around
be significantly lower than the band gap values of the pristine polymers reported in the
the N atoms of the amide NH- group as well as on the C=O groups of the Indigo dye. For
literature
Indigo-PPy, [14].
shownA similar
in Figureobservation of lowering
S1d, the charge was found of to
energy gap values
be concentrated was also
around the made in our
earlier
NH of PPystudies
and thepertaining
C=O groups to of
dyetheincorporation in for
Indigo dye, while polymers [14,15].
Indigo-PTh, shown The dye moieties have
in Figure
conjugated bondstoinbetheir
S1e, it was noticed structures,
centered andC=O
around the their incorporation
groups into
of Indigo and the
also oligomers/polymers
around the
C–C bondsconjugation,
enhances linked to the S which
group. lowers the energy gap values.

Molecules 2024, 29, x FOR PEER REVIEW 10 of 16

Figure Optimized
Figure 5.5.Optimized geometries
geometries of (a) Indigo-PANI,
of (a) Indigo-PANI, (b) PNA, (b) PNA, (c) Indigo-POPD,
(c) Indigo-POPD, (d)
(d) Indigo-PPy, Indigo-PPy, and
and
(e) Indigo-PTh,
(e) Indigo-PTh, Sulfur (yellow),
Sulfur Carbon
(yellow), (grey),(grey),
Carbon oxygen oxygen
(red), Nitrogen
(red), (blue), Hydrogen
Nitrogen (white).
(blue), Hydrogen (white).

The frontier molecular orbitals were computed to explore the changes in the bandgap
upon insertion of Indigo dimer in the oligomers. The highest occupied molecular orbital
(HOMO) of Indigo-PANI, shown in Figure 6a, was found to be evenly distributed over
the backbone of the dye moiety, while the lowest unoccupied molecular orbital (LUMO)
appeared to be less symmetric and completely distributed along the aniline ring. The
 age connecting the dye and the monomer molecule. The HOMO-LUMO energies were
computed to be 1.18 eV and 1.08 eV for Indigo-PPy and Indigo-PTh, respectively. The
incorporation of Indigo was found to result in variable HOMO-LUMO energy values,
which were found to be significantly lower than the band gap values of the pristine poly-
mers reported in the literature [14]. A similar observation of lowering of energy gap values
Molecules 2024, 29, 3200 was also made in our earlier studies pertaining to dye incorporation in polymers [14,15]. 10 of 15
The dye moieties have conjugated bonds in their structures, and their incorporation into
the oligomers/polymers enhances conjugation, which lowers the energy gap values.

Molecules 2024, 29, x FOR PEER REVIEW 11 of 16

Figure HOMO-LUMO
6.HOMO-LUMO
Figure 6. energies
energies ofIndigo-PANI,
of (a) (a) Indigo-PANI, (b) Indigo-PNA,
(b) Indigo-PNA, (c) Indigo-POPD,
(c) Indigo-POPD, (d) Indigo-(d) Indigo-
PPy, and
PPy, and (e)
(e)Indigo-PTh.
Indigo-PTh.

2.5. ComparisonofofExpermental
2.5. Comparison Expermentalandand Theoretical
Theoretical UV–Visible
UV–Visible SpectraSpectra
Thechanges
The changesinin thethe electronic
electronic transition
transition in theinoligomers
the oligomers upon incorporation
upon incorporation of Indigoof Indigo
dye were
dye werestudied
studied experimentally
experimentally as well
asaswell
theoretically, as shown in
as theoretically, asFigure
shown 7. The exper- 7. The
in Figure
imental UV–visible
experimental spectrum
UV–visible of pure Indigo
spectrum of pure dye revealed
Indigo dyepeaks at 250peaks
revealed nm, 350
at nm, and 350 nm,
250 nm,
600 nm (given in Figure S2 in the Supporting Information). The
and 600 nm (given in Figure S2 in the Supporting Information). The peaks in the peaks in the UV range areUV range
due to π-π*, while those in the visible range are due to n-π* transition.
are due to π-π*, while those in the visible range are due to n-π* transition. The spectrum The spectrum of of
PANI in the absence of Indigo (given in the inset) showed peaks at 275 nm and 400 nm,
PANI in the absence of Indigo (given in the inset) showed peaks at 275 nm and 400 nm,
while the experimental UV spectrum of Indigo-PANI, shown in Figure 7a, exhibited peaks
while the experimental UV spectrum of Indigo-PANI, shown in Figure 7a, exhibited peaks
at 280 nm in the UV range due to π-π* and at 500 nm in the visible range due to the n-π*
at 280 nm the
transition, in the UV
latter of range
which due toreferred
is also π-π* and at polaronic
to as 500 nm inband the [14].
visible range due to the n-π*
Polarons/bipolar-
transition, the latter of which is also referred to as polaronic band
ons are charge carrier defect states formed by p/n-type doping through the π-conjugated [14]. Polarons/bipolarons
are charge carrier defect states formed by p/n-type doping
backbone. The π-polaron band arises due to π-delocalization present in the conducting through the π-conjugated
backbone.
polymer. The The π-polaron
degree band arises
of delocalization due
will be to π-delocalization
greater present
if the conjugation in the and
increases conducting
polymer.
hence resultTheindegree of delocalization
the shifting of π-polaron bandwill be greater
towards if thewavelengths
higher conjugation[21].increases
The the-and hence
oreticalinspectrum
result also of
the shifting revealed
π-polaron peaksband
in the same range
towards highershowing an oscillator
wavelengths [21].strength
The theoretical
value of 0.33
spectrum forrevealed
also the polaronic
peakspeak. Thesame
in the shifting
rangeof the polaronic
showing an peak was due
oscillator to the value of
strength
greater
0.33 forextent of conjugation
the polaronic peak. induced by theofinsertion
The shifting of Indigo
the polaronic dye.was
peak ThedueUV to
spectrum of extent
the greater
Indigo-PNA, shown in Figure 7b, displayed peaks at 285 nm, and a broad
of conjugation induced by the insertion of Indigo dye. The UV spectrum of Indigo-PNA, hump spanning
between 500 and 700 nm and the theoretical spectrum of Indigo-PNA revealed the n-π*
shown in Figure 7b, displayed peaks at 285 nm, and a broad hump spanning between 500
transition peak at 500 nm, with an oscillator strength value of 0.70. The spectrum of PNA
and 700 nm and the theoretical spectrum of Indigo-PNA revealed the n-π* transition peak
in the absence of Indigo revealed peaks at 250 nm and 500 nm. Likewise, The UV spectrum
at 500 nm, with an oscillator strength value of 0.70. The spectrum of PNA in the absence
of POPD in the absence of Indigo showed a pronounced peak at 350 nm, whereas the
experimental UV spectrum of Indigo-POPD, shown in Figure 7c, revealed peaks at 250
nm and 400 nm. The theoretical spectrum of the same oligomer revealed a pronounced
peak at 400 nm with an oscillator strength value of 1.4 [10]. This intense peak corre-
sponded to the n-π* transition. The UV spectra of Indigo-PPy and Indigo-PTh (shown in
Figure 7d,e) displayed peaks at 250 nm, 500 nm, and 700 nm, corresponding to π -π* and
 Molecules 2024, 29, 3200 11 of 15

of Indigo revealed peaks at 250 nm and 500 nm. Likewise, The UV spectrum of POPD in
the absence of Indigo showed a pronounced peak at 350 nm, whereas the experimental UV
spectrum of Indigo-POPD, shown in Figure 7c, revealed peaks at 250 nm and 400 nm. The
theoretical spectrum of the same oligomer revealed a pronounced peak at 400 nm with an
oscillator strength value of 1.4 [10]. This intense peak corresponded to the n-π* transition.
The UV spectra of Indigo-PPy and Indigo-PTh (shown in Figure 7d,e) displayed peaks
at 250 nm, 500 nm, and 700 nm, corresponding to π -π* and n-π* transitions, respectively.
The theoretical spectra showed n-π* transitions matching the experimental spectra. The
oscillator strength for the 500 nm peak in Indigo-PPy was computed to be 0.45, while
the oscillator strength for the 700 nm peak in Indigo-PTh was computed to be 0.25. The
Molecules 2024, 29, x FOR PEER REVIEW
oligomers showed variation in the electronic transitions upon modification with Indigo 14 of 17
dye, which suggests that desirable electronic transitions could be achieved by varying the
monomer and incorporating Indigo dimer [13,14]. The experimental and theoretical data
were found to be in close agreement with each other for all the dye-modified oligomers.

7. UV-Vis
Figure 7.
Figure UV-Visspectra
spectraofof(a)
(a)Indigo-PANI,
Indigo-PANI, (b)(b)
Indigo-PNA,
Indigo-PNA, (c) (c)
Indigo-POPD,
Indigo-POPD,(d) Indigo-PPy, and and
(d) Indigo-PPy,
(e) Indigo-PTh.
(e) Indigo-PTh.(inset
(insetininFigures
Figuresrefers toto
refers UV spectra
UV of pristine
spectra olymers
of pristine in absence
olymers of Indigo
in absence dye).dye)
of Indigo

2.6. Comparison of Experimental and Computational Vibrational Spectra

The IR spectral data of Indigo-PANI (given in Table S1 and Figure S3a–e in the Sup-
plementary Information) showed characteristic peaks at 3258 cm−1 and 3032 cm−1 corre-
−1
Molecules 2024, 29, 3200 12 of 15

2.6. Comparison of Experimental and Computational Vibrational Spectra

The IR spectral data of Indigo-PANI (given in Table S1 and Figure S3a–e in the Sup-
plementary Information) showed characteristic peaks at 3258 cm−1 and 3032 cm−1 cor-
responding to the N–H stretching vibration. The peak at 1620 cm−1 was ascribed to
carbonyl stretching (C=O), while the peak at 1613 cm−1 was attributed to C=C conju-
gated alkene stretching [13–15]. The C=C quinonoid stretching peaks were observed at
1585 cm−1 , 1483 cm−1 , and 1456 cm−1 , and the C=C benzenoid stretching peaks were
seen at 1390 cm−1 , 1336 cm−1 , 1313 cm−1 , and 1298 cm−1 . Multiple peaks at 1256 cm−1
and 1219 cm−1 were correlated with the C–N stretching vibration mode. The character-
istic peaks at 1198 cm−1 , 1170 cm−1 , 1124 cm−1 , 1104 cm−1 , 1092 cm−1 , 1065 cm−1 , and
1010 cm−1 were correlated with the C–H bending mode. Aromatic ring stretching vibra-
tions were noticed between 934 cm−1 and 656 cm−1 . The IR spectral data of Indigo-PNA
revealed the N–H stretching peak at 3249 cm−1 and 3056 cm−1 . The peak at 1623 cm−1 was
ascribed to carbonyl stretching (C=O), and the peak at 1610 cm−1 was correlated with the
C=C conjugated alkene stretching [14,15]. The C=C quinonoid stretching peaks appeared
at 1586 cm−1 , 1482 cm−1 , and 1460 cm−1 , while the C=C benzenoid peaks were found at
1391 cm−1 , 1334 cm−1 , 1315 cm−1 , and 1296 cm−1 . The C–N stretching peak was noticed
at 1222 cm−1 , while the presence of multiple peaks between 1186 cm−1 and 1006 cm−1
were correlated with C–H bending. Aromatic ring stretching vibrations were noticed
between 946 cm−1 and 662 cm−1 [13–15]. The IR spectral data of Indigo-POPD showed
N–H stretching peaks at 3258 and 3032 cm−1 and the carbonyl stretching (C=O) peak at
1622 cm−1 . C=C quinonoid stretching peaks were noticed at 1586 cm−1 , 1482 cm−1 , and
1457 cm−1 , while C=C benzenoid peaks showed up at 1389 cm−1 , 1337 cm−1 , 1317 cm−1 ,
and 1297cm−1 . C–N stretching peaks appeared at 1249 cm−1 and 1221 cm−1 . C–H bending
peaks were found between 1198 cm−1 and 1009 cm−1 , while aromatic ring stretching vibra-
tions were noticed between 940 cm−1 and 664 cm−1 . The IR spectral data of Indigo-PPy
showed the N–H stretching characteristic peak at 3268 cm−1 , while the C=O stretching
peak appeared at 1625 cm−1 . C=C stretching peaks were seen between 1585 and 1298 cm−1 .
C–N stretching peaks were found at 1254 cm−1 and 1220 cm−1 . Similar peaks were noticed
in the case of Indigo-PTh. The presence of multiple NH stretching peaks, C=O stretching,
CN vibration peaks, and quinonoid/benzenoid peaks confirmed the polymerization and
successful modification of the polymer with Indigo dye [13–15]. It was interesting to note
that the theoretical data closely matched the experimental values, which confirmed the
proposed structures of the polymers, as depicted in Scheme 1a–e.

3. Conclusions
Indigo-dimer-incorporated oligomers of PANI, PNA, POPD, PPy, and PTh were suc-
cessfully synthesized via an ultrasound-assisted technique. The XRD results confirmed
the semi-crystalline characteristics of the oligomers, and SEM revealed a remarkable trans-
formation of the morphology from a flaky to mixed morphology of granules and rod-like
structures upon incorporating Indigo dye. Fluorescence emission was observed to be in the
near-infrared region for Indigo-PTh and around the visible region for the other oligomers.
The theoretical results obtained using DFT studies were observed to be in close agreement
with the experimental IR as well as UV data. The frontier molecular orbital distribution
showed a reduction in HOMO-LUMO energy upon the incorporation of Indigo dye. This
technique is a facile way of introducing multifunctionality in oligomers/polymers via the
incorporation of dyes that usually have a conjugated architecture. This method could be
applied in designing near-infrared-light-emitting probes utilized in photodynamic therapy.

4. Experimental Section
Indigo (GLR Innovations, New Delhi, India), chloroform (Merck, New Delhi, India),
ferric chloride (Merck, New Delhi, India), thiophene (Loba Chemie Pvt. Ltd., New Delhi,
India), pyrrole (Merck, New Delhi, India), Aniline (Sigma Aldrich, St. Louis, MI, USA),
ortho-phenylenediamine (Sigma Aldrich, St. Louis, MI, USA), 1-naphthylamine (Loba
Molecules 2024, 29, 3200 13 of 15

Chemie Pvt. Ltd., Maharashtra, India), dimethyl sulfoxide (DMSO) (Merck, New Delhi,
India), dimethylformamide (DMF) (S.d. Fine Chem., Pvt. Ltd., New Delhi, India), N-
Methyl-2-pyrrolidone (NMP) (Merck, New Delhi, India), and distilled water were used
without further purification.

4.1. Synthesis of Indigo-Dye-Incorporated Polymers

Aniline (40 mL, 4.3 × 10−1 mol) dissolved in chloroform (50 mL) was added to a
round-bottom flask (250 mL) containing Indigo dye (5 g, 1.9 × 10−2 mol) and sonicated
in an ultrasonic bath (model Scope Enterprises Pvt. Ltd., India) between 0 ◦ C and 5 ◦ C.
Ferric chloride (3.1 g, 1.9 × 10−2 mol) was added as an initiator to the reaction mixture and
further sonicated for 5 h at the same temperature. The obtained polymer was then kept in a
deep freezer for 24 h at −5 ◦ C and subsequently centrifuged, washed several times with
distilled water using an R-8C laboratory centrifuge, and dried in a vacuum oven for 24 h
at 70 ◦ C. The same reaction was carried out using 1-naphthylamine, o-phenylenediamine,
pyrrole, and thiophene, and the synthesized polymers were designated as poly Indigo-
PANI, Indigo-PNA, Indigo-POPD, Indigo-PPy, and Indigo-PTh, as shown in Scheme 1a–e.
(% yield: Indigo-PANI: 88%, Indigo-PNA: 82%, Indigo-POPD: 78%, Indigo-PPy: 76%, and
Indigo-PTh: 80%; solubility: partially soluble in ethanol, methanol, chloroform, and H2 O
and completely soluble in dimethylsulphoxide (DMSO), N-methyl pyrrolidone (NMP), and
dimethyl formamide (DMF).)

4.2. Characterization
4.2.1. Spectral Analysis
IR spectra of conjugated polymers were obtained using an FT-IR spectrophotometer
(Shimadzu, Model IRA Affinity-1, Kyoto, Japan), while ultraviolet–visible light (UV-vis)
spectra were recorded using a UV-vis spectrophotometer (Shimadzu UV-1800, Kyoto,
Japan), using a water/NMP mixture as a solvent. Fluorescence studies were performed
using a fluorescence spectrophotometer (Fluorolog @ 3-11, Bengaluru, India), using wa-
ter/NMP as a solvent.

4.2.2. Morphological Analysis

XRD patterns of the conjugated polymers were recorded on Malvern Pananalytical,
(USA Philips model PW 3710 2400 Computer Drive, Suite 2100, Westborough, MA, USA)
using Ni-filtered Cu-Kα radiation. TEM micrographs were obtained using a Morgagni
model 268-D TEM system (Hillsboro, OR, USA).

4.2.3. Thermal Analysis

TGA analyses of the polymers were carried out using STA 6000 (Perkin Elmer In-
struments, Shelton, CT, USA) at a heating rate of 10 °C/min over a temperature range of
50–800 ◦ C in a nitrogen atmosphere.

4.2.4. DFT and TD-DFT Calculations

The calculations were performed using GAUSSIAN 09 software(Wallingford, USA)
and the optimized geometries were obtained using DFT/B3LYP method with the 6-311G
(d,p) basis set [12,13]. The oscillator strength, HOMO-LUMO energies, and band gap were
determined using the optimized geometries with the same basis set. The same optimized
structures were used in the vibrational frequency calculations. The UV−vis spectra of
the geometry-optimized structures were simulated at TD-DFT/B3LYP using 6-311G (d,p)
basis set.
Molecules 2024, 29, 3200 14 of 15

Supplementary Materials: The following are available online at https://www.mdpi.com/article/10

.3390/molecules29133200/s1. Figure S1: Muliken charge distribution in (a) Indigo-PANI, (b) Indigo-
PNA, (c) Indigo-POPD, (d) Indigo-PPy, (e) Indigo-PTh, Figure S2: UV visible spectrum of pure
Indigo dye, Figure S3: experimental and theoretical IR spectra of (a) Indigo-PANI, (b) Indigo-PNA,
(c) Indigo-OPD, (d) Indigo-PPy, (e) Indigo-PTh, Table S1: IR spectra data of Indigo-PANI, Indigo-PNA,
Indigo-POPD, Indigo-PPy and Indigo-PTh.
Author Contributions: Conceptualization, U.R.; methodology, N.S.; software, T.D.; validation, U.R.;
formal analysis, T.D.; investigation, N.S.; resources, U.R.; data curation, N.S.; writing—original draft
preparation, N.S.; writing—review and editing, U.R.; supervision, U.R.; project administration, U.R.;
All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Data is included in the manuscript and supporting information.
Acknowledgments: The corresponding author Ufana Riaz wishes to acknowledge the Faculty Re-
search Awards Program (FRAP) for providing financial assistance. Tionna Douglas wishes to ac-
knowledge the National Science Foundation (Award # 2122044) and the NSF PREM for Hybrid
Nanoscale Systems between NCCU and Penn State for providing financial assistance. Neetika Singh
acknowledges the SERB—National Postdoc Fellowship (NPDF) F.No. PDF/2022/000556, DST, India
for providing financial support.
Conflicts of Interest: The authors declare no conflicts of interest.

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