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Acidochromic Behavior of Dibenzylidene Cyclohexanone-Based

Bischalcone: Experimental and Theoretical Study
Md Mizanur Rahman Badal,* Hasan Md Ashekul Islam, Md Maniruzzaman,
and Mahammad Abu Yousuf
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ABSTRACT: Synthesis and characterization of substituted 2,6-dibenzylidene cyclo-

hexanone-based bischalcone derivatives and their optimized geometries were investigated
by density functional theory. The synthesized compounds were identified through
ultraviolet−visible, Fourier transform infrared, and 1H nuclear magnetic resonance
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spectroscopies and elemental analysis. Significant acidochromic behavior was observed for
2,6-bis(4-dimethylamino-benzylidene)-cyclohexanone 1e. This result is owing to the
preferential protonation of the chromophoric N,N-dimethylamino group, that is,
quaternary salt formation and deactivation of the resonance system. The result was
consistent with computational studies where the protonation was favored by 211 kcal/mol in the gas phase. The compounds also
showed solvatochromic behavior. The geometries of the synthesized compounds were optimized with B3LYP/6-311G+(d,p) and
APFD/6-311+G(d,p) basis sets. The single point energy indicated that APFD/6-311+G(d,p) basis set gave the lowest energy of
445−655 kcal/mol for the studied bischalcone derivatives. Quantum chemical parameters were also calculated.

■ INTRODUCTION
Dibenzylidene-cyclohexanone is a cyclohexanone-based bis-
the carbonyl compounds is liable for the biological activities of
chalcones. The photophysical and optical properties of various
chalcone that possesses two reactive keto-vinyl moieties substituted bischalcones have been studied.17,18 These
(−CO−CHCH−) and hence are categorized as bichromo- compounds can also be used in several optical devices
phoric molecules.1,2 Bischalcones possess a system of including fluorescent-based DNA assays, photoalignment
conjugated double bonds on both of the benzene rings and a layer of liquid crystal display, and metal ions.19 Therefore, it
completely delocalized electron system. Because of the is a challenge to synthesize this lucrative-substituted
presence of this chromophoric group, these compounds are bischalcone derivative in a solvent-free method with high
very fascinating for researchers to develop new compounds.3,4 yield, as well as its stability should be thoroughly checked. In
Similarly, one of the simple natural occurring chemical
this study, substituted dibenzylidine-cyclohexanone-based
constituents, chalcones, found in lower kingdoms to higher
plants, are considered to be precursors of flavonoids and bischalcones were synthesized as shown in Scheme 1.
isoflavonoids.5,6 Both natural and synthetic chalcones have
attracted a great deal of interest among scientists and Scheme 1. Preparation of Substituted 2,6 Dibenzylidene-
researchers for their important biological activities. In tradi- cyclohexanones
tional medical treatment, chalcone-containing plants have been
used so far.7−9 For pharmacological studies, chalcones have
been isolated from different plants, and their clinical test for
ailment of cancer, viral, and cardiovascular diseases has been
done. Later, it was confirmed that these compounds display
biological activities such as antiviral, antitumor, antitubercular,
anticancer, anti-inflammatory, and antifungal and inhibit
tyrosinase.10−13 On the other hand, the chromophoric group
that is responsible for the change of color of compounds on
interaction with acids, known as acidochromism, has a Received: May 30, 2020
significant role in the sensor industry.14,15 These types of Accepted: August 14, 2020
compounds have shown wide range of acidochromism Published: August 28, 2020
behavior. The significant use of these compounds is as
inhibitors of pulmonary carcinogens and ovarian cancer cell
proliferation.16 Basically, the presence of α,β-unsaturation of

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsomega.0c02556

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The structure of the compounds was identified by
ultraviolet−visible (UV−vis), Fourier transform infrared
(FTIR), and 1H nuclear magnetic resonance (NMR) spectros-
copies and elemental analysis. Acidochromic behavior and
solvatochromic behavior were examined with various solvents
to explicate the interaction parameters. A computational study
was carried out by the density functional theory (DFT)
method. The geometries were optimized by both B3LYP/6-
311G+(d,p) and APFD/6-311+G(d,p) basis sets. The
quantum chemical parameters and frontier molecular orbitals
were also calculated.
■ RESULTS AND DISCUSSION
Spectroscopic Properties. The spectroscopic properties
of the synthesized 2,6 dibenzylidene-cyclohexanone derivatives
1a−1e were examined using UV−vis spectroscopy. The
synthesized products were soluble in most organic solvents,
and the absorption maxima in ethanol ranging from 330 to 452
nm are shown in Table 1.
Table 1. Absorbance of Substituted 2,6 Dibenzylidene-
cyclohexanone in Ethanol
substituents (X) H p-Cl p-NO2 p-OCH3 p-N(CH3)2
wavelength, λmax (nm) 330 333 340 359 452
The synthesized product 2,6-dibenzylidene-cyclohexanone
1a showed absorption maxima at 330 nm, whereas 2,6-bis(4-
dimethylamino-benzylidene)-cyclohexanone 1e showed high
absorption maxima at 452 nm, as shown in Figure 1.
Figure 1. UV−vis spectrum of compounds 1a−1e in ethanol.
The bathochromic shift induced for compound 1e,
compared with other synthesized products, is because the
electron-donating N,N-dimethylamino substituents interact
with electron-accepting moieties that might be stabilized by
an internal charge transfer assisted by the lone pair of carbonyl
oxygen. Compound 1a showed hypsochromic shifts compared
to compound 1e for its basic chalcone framework. Because it
has no substituent, no substituent effect was observed.
Similarly, the compound 2,6-bis(4-methoxy-benzylidene)-
cyclohexanone 1d showed a bathochromic shift (absorption
maxima at 359 nm) which is lesser than that of compound 1e
because of the presence of the electron-donating methoxy
(−OCH3) substituent. The presence of the electron-with-
drawing substituent in 1b and 1c (containing halogen and
nitro substituents) contributed very little effect to the
absorption maxima at 333 and 340 nm, respectively. These
findings may explain that the electronegativity of the carbonyl
oxygen of bischalcone is cancelled by the interaction of these
electron-withdrawing groups.
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Acidochromic Properties. Acidochromic behavior of the
investigated compound 2,6-bis(4-dimethylamino-benzyli-
dene)-cyclohexanone 1e was explored at different hydrogen
concentrations using hydrochloric acid (HCl), as shown in
Figure 2.
Figure 2. UV−vis spectrum of compound 1e in ethanol with 0.02−
0.11 M hydrochloric acid.
The result revealed that on increasing the concentration of
hydrochloric acid, hypochromic shifts (n → π*) occur, and
with time, the absorption maxima at 452 nm gradually
decreases, while a new absorption band at 322 nm gradually
appears and becomes sharper. This change is due to the
characteristics protonation of the chromophoric N,N-dimethy-
lamino group and the formation of quaternary salt, as shown in
Scheme 2. This quaternary system deactivates the π-electron
delocalization, resulting in the absorption maxima shift to 322
nm.
Scheme 2. Quaternary Salt Formation of 2,6-Bis(4-
dimethylamino-benzylidene)-cyclohexanone
On the other hand, for the synthesized 2,6-bis(4-methoxy-
benzylidene)-cyclohexanone 1d, there is no shift in wavelength
when treated with protic acid, though the absorption maxima
decreased a little, which is shown in Figure 3. This result is
Figure 3. UV−vis spectrum of compound 1d in ethanol with 0.02−
0.06 M hydrochloric acid.
contradictory to the findings of Bedekar et al.,20 where they
have shown that in the presence of protic acid, a bathochromic
shift was observed with a clear color change from yellow to red.
Probably, the decreases in absorption maxima were observed
mainly due to the decrease of concentration of the compound
on adding the acid. Similar behaviors were observed for other
substituted bischalcone-based cyclohexanone.
Solvatochromic Properties. The solute−solvent inter-
actions usually play a vital role for a given solute. The UV−vis
absorption maxima is shifted for different solvents of the
studied compounds. This solvatochromic behavior is fascinat-
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ing to explore the properties of the ground state of a molecule.
The experimental absorption maxima is shown in Figure 1, and
the values are summarized with the computational results in
Table 2. The findings indicate that the bathochromic shift was
Table 2. Solvent Effect of Substituted 2,6 Dibenzylidene-
cyclohexanone
dichloromethane
(nm) ethylacetate (nm) ethanol (nm)
substituents (X) exp. calc.a exp. calc.a exp.
H 308 360 323.5 359 330
p-Cl 333 366 328.5 367 333
p-NO2 340 357 336 352 340
p-OCH3 340.5 367 352 376 359
p-N(CH3)2 358.5 391 421.5 391 452
a
Calculated at TD-SDF/DFT/B3LYP/6-311G+(d,p).
observed for all substituted 2,6-dibenzylidene-cyclohexanones
with increasing polarity of the solvent, with the exception of 1b
and 1c.
These results showed the decrease the energy of the excited
state with the increase in the polarity of the solvent, which is in
the order of dichloromethane < ethyl acetate < ethanol. This
behavior revealed that the molecules in the ground state as well
as the excited state were dissimilar in different polarities. The
examined compounds with nonpolarized ground state were
highly polarized in protic solvents, causing the high energy
polar structure of the excited state to be stabilized.
Consequently, the excited state was lowered, and at the same
time, the ground state was scarcely affected. The computa-
tionally calculated absorption maxima showed the general
approach of the substituent effect that reflects the experimental
results with the studied solvents. Most remarkably, the
calculated solvatochromic behavioral trend is reliable and
replicate the experimental results, though the magnitude of the
absorption maxima among the solvents is small.
■
COMPUTATIONAL RESULTS
Single Point Energies. Single point energies of the
optimized structures 1a−1e were calculated at the B3LYP/6-
311+G(d,p) and APFD/6-311+G(d,p) level of theories. All
examined compounds showed that APFD/6-311+G(d,p) level
of theories gave the lowest energy, and the value was lower
than 445−655 kcal/mol. Single point energies for compounds
1a−1e are given in Table S7 (Supporting Information).
Geometric Parameter Analysis. Several geometric
parameters, for example, bond lengths, bond angles, and
dihedral angles were measured computationally at the APFD/
6-311+G(d,p) level of theories. Among the studied com-
pounds, one of the optimized structures of 2,6-bis(4-
dimethylamino-benzylidene)-cyclohexanone is given in Figure
4.
The calculated values for the studied compounds are given
in Table 3. The bond distance of O26−C3 is found
significantly shorter for para-nitro-substituted bischalcones
compared to others because of its strong electron-withdrawing
capacity. Both the benzene rings are ordinary hexagonal shape,
with C−C bond lengths (1.40 Å) somewhat in between the
typical values for a single bond (1.54 Å) and a double (1.33 Å)
bond.21 The two C−C bonds (connecting benzene ring) are
shorter than the normal sp3−sp2 C−C bond because of the
long-range effect of the electron-withdrawing group. The C
Article
Figure 4. Optimized structure of 2,6-bis(4-dimethylamino-benzyli-
dene)-cyclohexanone at APFD/6-311+G(d,p) level of theories.
calc.a
361
C bonds connecting with the cyclohexane ring are somewhat
368
longer than the normal CC bond because of the
357
delocalization of the π-electron. From the investigation of
376
bond lengths, it is clear that there is a dual electronegative
392
interaction between the carbonyl oxygen and the other
electron-withdrawing group viz. nitro group or chloride
attached to the benzene ring. Dihedral angles of a molecule
provided information about planarity. Usually dihedral angle
values of 0, 180, or 360° show the planarity of a molecule.22 In
the respective bischalcones, O26−C3−C4−C14 dihedral angle
of 1.520 (1a), 0.999 (1b), −1.573 (1c), 0.964 (1d), and 1.304
(1e) and C3−C4−C14−C16 dihedral angle of −179.3 (1a),
−179.2 (1b), −179.6 (1c), −178.5 (1d), and −178.2 (1e)
indicated a slight distortion from planarity. It is revealed that
the CC bonds attached to the benzene ring are in-plane but
are slightly distorted due to the fixed cyclohexane ring in both
sides. In contrast to the protonated form of compound 1e, the
dihedral angle of O26−C3−C4−C14 is −4.245. It clearly
indicates that the protonated form is significantly distorted
from planarity and deactivates the conjugation of the π-
electron. This finding was consistent with the experimental
result, where a hypsochromic shift for compound 1e was
observed in the presence of the acid.
Global Reactivity Descriptors and Calculated Frontier
Molecular Orbitals. Frontier molecular orbital analysis is
convenient in expecting the electronic transition involved in
the conjugated system as well as its reactivity.23 The highest
occupied molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) calculations were performed at the
same level of theories. The energies of HOMO and LUMO for
the studied compounds and the three-dimensional frontier
molecular orbital schemes are shown in Figure 5.
It showed that the HOMO and LUMO are located on the
whole molecule. Therefore, it exposed that conjugation is
predominantly observed for the molecules. According to the
quantum theory, the hard molecule has a high HOMO−
LUMO gap, whereas a soft molecule has a small HOMO−
LUMO gap. In the perception of chemical reactivity, the soft
molecules having a small gap would be more reactive than the
hard molecules. For the studied bischalcones, compound 1e
having a small value of HOMO−LUMO gap indicates a soft
molecule with high reactivity and hence promotes eventual
charge transfer (CT) interactions within the molecules. Figure
6 shows the contour structure of 2,6-bis(4-dimethylamino-
benzylidene)-cyclohexanone that revealed the delocalization of
the π-electron.
The EHOMO energy corresponds to ionization energy (I) and
the ELUMO energy is for electron affinity (A) according to Parr
and Nitti.24,25 Quantum chemical parameters such as
ionization potential (I), electron affinity (A), chemical
hardness (η), electronic potential (μ), electronegativity (χ),
chemical softness (S), and electrophilicity index (ω) were
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Table 3. Selected Bond Lengths, Bond Angles, and Dihedral Angles of Compounds 1a−1e Calculated at the APFD/6-
311+G(d,p) Level of Theories
substituents
bond lengths(angstrom) H p-Cl p-NO2 p-OCH3 p-N(CH3)2
O26−C3 1.225 1.225 1.221 1.227 1.228
C3−C2 1.508 1.508 1.509 1.505 1.501
C2−C13 1.352 1.352 1.348 1.354 1.352
C13−C27 1.454 1.463 1.462 1.460 1.454
C27−C29 1.408 1.408 1.407 1.405 1.406
C29−C32 1.390 1.389 1.384 1.391 1.381
C32−C34 1.395 1.392 1.389 1.398 1.411
C34−O47(N38)(Cl38) 1.756 1.472 1.351 1.383
O47−(N38)C42(C48) 1.423 1.453
C3−C4 1.508 1.508 1.509 1.505 1.501
C4−C14 1.352 1.352 1.348 1.354 1.352
C14−C16 1.454 1.463 1.462 1.460 1.454
C16−C17 1.408 1.408 1.407 1.405 1.406
C17−C19 1.390 1.389 1.384 1.391 1.381
C19−C23 1.395 1.392 1.389 1.398 1.411
C23−O46(N39)(Cl38) 1.756 1.472 1.361 1.383
C46−O38 1.423
Bond Angles (deg)
O26−C3−C4 120.65 120.66 120.61 120.68 120.69
C3−C4−C14 115.75 115.66 115.29 115.75 115.87
Dihedral Angles (deg)
O26−C3−C4−C14 1.720 0.999 −2.573 0.964 −1.904
C3−C4−C14−C16 −179.3 −179.2 −179.6 −178.5 −178.2

Figure 6. Contour structure of 2,6-bis(4-dimethylamino-benzyli-

dene)-cyclohexanone at APFD/6-311+G(d,p) level of theories.

Figure 5. Frontier molecular orbital distributions and energy levels for
compounds 1b−1e characterized by APFD/6-311+G(d,p) level of
theories.
determined according to the literature.26 Quantum chemical
parameters for compounds 1a−1e are χ = −μ = 4.42, 4.61,
5.41, 4.01, and 3.52 eV; η = 1/S = 1.96, 1.90, 1.86, 1.82, and
1.64 eV; and ω = 1/ε = 4.98, 5.58, 7.88, 4.42, and 3.54 eV,
respectively. According to these parameters, the chemical
reactivity varies with the substituent of bischalcones.
22981
■ EXPERIMENTAL SECTION
All starting materials and reagents were purchased and used
without additional purification unless otherwise noted. UV−vis
spectra of the samples were recorded on a UV-180
SHIMADZU spectrophotometer. FTIR spectra of the samples
were measured on the IRTracer-100, SHIMADZU, Japan. 1H
NMR spectra of the samples were measured with an AVANCE
Bruker NMR spectrometer at 400 MHz using CDCl3 as the
solvent and trimethyl silane as an internal standard. The
elemental analysis was performed using a CE-440 elemental
analyzer, Exeter Analytical, Inc.
General Procedure for the Synthesis of Compounds
1a−1e.20 A mixture of 1.0 equiv of cyclohexanone, 2.0 equiv
of substituted benzaldehyde, and 2.2 equiv of solid NaOH
were ground in a mortar for about 30 min at room
temperature. The progress of the reaction was monitored by
thin-layer chromatography. After the reaction was completed,
dilute hydrochloric acid (HCl) was poured carefully for
neutralizing the mixture. The obtained solid products were
filtered and dried on air. The crude product was purified by
recrystallization.
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2,6 Dibenzylidene-cyclohexanone (1a). Yellow powder,
mp 106 °C, yield 94%. The IR (KBr) spectrum of the product
(ν cm−1): 3022, 2950, 2933, 1661, 1574, 1443, 1434. 1H NMR
(400 MHz CDCl3): δ 1.82−1.76 (m, 2H, CH2), 2.93 (t, J =
14.4 Hz, 4H, 2 × CH2), 7.34 (t, J = 14.4 Hz, 2H, Ar), 7.41 (t, J
= 14.4 Hz, 4H, Ar), 7.47 (d, J = 7.4 Hz, 4H, Ar), 7.80 (s, 2H,
allylic). Anal. Calcd for C20H18O (274.36): C, 87.56; H, 6.61;
O, 5.83. Found: C, 87.31; H, 6.42; O, 5.75.
2,6-Bis(4-chloro-benzylidene)-cyclohexanone (1b). Yel-
lowish green powder, mp 124 °C, yield 89%. The IR (KBr)
spectrum of the product (ν cm−1): 2964, 2927, 1667, 1585,
1576, 1465, 1265, 1160, 821, 800. 1H NMR (400 MHz
CDCl3): δ 1.84−1.77 (m, 2H, CH2), 2.91−2.87 (m, 4H, 2 ×
CH2), 7.38−7.25 (m, 8H, Ar), 7.73 (s, 2H, allylic). Anal. Calcd
for C20H16Cl2O (343.25): C, 69.98; H, 4.70; Cl, 20.66; O,
4.66. Found: C, 69.62; H, 4.54; O, 4.51.
2,6-Bis(4-nitro-benzylidene)-cyclohexanone (1c). Light
brown powder, mp 172 °C, yield 91%. The IR (KBr) spectrum
of the product (ν cm−1): 2923, 2850, 1669, 1599, 1517, 1491,
1345, 1300, 1268, 1160. 1H NMR (400 MHz CDCl3): δ 1.88−
1.82 (m, 2H, CH2), 2.94 (t, J = 10.3 Hz, 4H, 2 × CH2), 7.59
(d, J = 8.7 Hz, 4H, Ar), 7.81 (s, 2H, allylic), 8.24 (d, J = 8.7,
4H, Ar). Anal. Calcd for C20H16N2O5 (364.35): C, 65.93; H,
4.43; N, 7.69; O, 21.96. Found: C, 65.72; H, 4.38; N, 7.59; O,
21.82.
2,6-Bis(4-methoxy-benzylidene)-cycloexanone (1d). Pale
yellow powder, mp 152 °C, yield 88%. The IR (KBr) spectrum
of the product (ν cm−1): 2938, 2827, 1657, 1595, 1199, 1184,
870, 837. 1H NMR (400 MHz CDCl3): δ 1.84−1.78 (m, 2H,
CH2), 2.92 (t, J = 14.2, 4H, 2 × CH2), 3.85 (s, 6H, 2×CH3O),
6.93 (d, J = 8.7 Hz, 4H, Ar), 7.45 (d, J = 8.7 Hz, 4H, Ar), 7.76
(s, 2H, allylic). Anal. Calcd for C22H22O3 (334.41): C, 79.02;
H, 6.63; O, 14.35. Found: C, 78.95; H, 6.53; O, 14.22.
2,6-Bis(4-dimethylamino-benzylidene)-cyclohexanone
(1e). Yellow powder, mp 136 °C, yield 79%. The IR (KBr)
spectrum of the product (ν cm−1): 2926, 2853, 1645, 1609,
1361, 1302, 1157, 871, 818. 1H NMR (400 MHz CDCl3): δ
1.83−1.79 (m, 2H, CH2), 2.94 (t, J = 14.1, 4H, 2 × CH2), 3.01
(s, 12H, 2 × N (CH3)2), 6.71 (d, J = 8.8 Hz, 4H, Ar), 7.45 (d,
J = 8.8 Hz, 4H, Ar), 7.76 (s, 2H, allylic). Anal. Calcd for
C24H28N2O (360.49): C, 79.96; H, 7.83; N, 7.77; O, 4.44.
Found: C, 79.82; H, 7.74; N, 7.54; O, 4.38.
Computational Details. DFT and time-dependent DFT
were calculated using the B3LYP functional combined with the
Becke’s three-parameter hybrid functional27 and the non-local
correlation functional of LYP.28−30 The structures were
optimized by the B3LYP/6-311G+(d,p) and APFD/6-311G
+(d,p) basis set. The harmonic vibrational frequencies were
performed at the same level of theory to find out the local
minima for the stationary points. All calculations were done
using Gaussian 16, Revision C.01 series of programs.
■
CONCLUSIONS
Substituted 2,6-dibenzylidene cyclohexanone-based bischal-
cone derivatives were synthesized, and their structure was
determined using UV−vis, FTIR, and NMR spectroscopies
and elemental analysis. Significant acidochormic behavior was
noticed for 2,6-bis(4-dimethylamino-benzylidene)-cyclohexa-
none. The absorption maxima shifted from 452 to 322 nm
because of the characteristics protonation of the chromophoric
N,N-dimethylamino group and the formation of quaternary
salt, making the ring strongly deactivated. The result was
consistent with computational studies. The synthesized
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Article
compounds showed solvatochromic behavior. These results
indicate that an intramolecular CT occurred because of
electron donor−acceptor moieties of the synthesized com-
pounds. A significant bathochromic shift was found for
compounds 1a, 1d, and 1e in the increasing order of
dichloromethane < ethylacetate < ethanol. These substituents
showed positive solvatochromism for (n → π*) absorption in
ethanol, whereas a negative solvatochromism was observed (π
→ π*) for the polar aprotic solvent. Compounds 1b and 1c
deviated from this trend and explains that the electronegativity
of the carbonyl oxygen of bischalcone is cancelled by the
interaction of the electron-withdrawing groups. Computational
results revealed that the substituents impart a vital role for its
reactivity because of the planarity and effective conjugation.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.0c02556.
Cartesian coordinates of the optimized structure and
single point energies of different substituted 2,6
dibenzylidene-cyclohexanones at the APFD/6-311+G-
(d,p) level (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Md Mizanur Rahman Badal − Department of Chemistry,
Khulna University of Engineering and Technology, Khulna
9203, Bangladesh; orcid.org/0000-0002-4119-4337;
Phone: +8801714087278; Email: mizan@chem.kuet.ac.bd
Authors
Hasan Md Ashekul Islam − Department of Chemistry, Khulna
University of Engineering and Technology, Khulna 9203,
Bangladesh
Md Maniruzzaman − Department of Chemistry, Khulna
University of Engineering and Technology, Khulna 9203,
Bangladesh
Mahammad Abu Yousuf − Department of Chemistry, Khulna
University of Engineering and Technology, Khulna 9203,
Bangladesh
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.0c02556
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge the Khulna University of Engineer-
ing and Technology for financial support and necessary
facilities. The authors are also grateful to Prof. Dr. Manabu
Abe, Graduate School of Advanced Science and Engineering,
Hiroshima University, Japan, for supporting the NMR analysis.
■
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22983 https://dx.doi.org/10.1021/acsomega.0c02556
ACS Omega 2020, 5, 22978−22983