Synthesis and DFT calculations of linear and nonlinear optical responses of novel 2-thioxo-3-N,(4-methylphenyl) thiazolidine-4 one

Article abstract of DOI:10.1080/17415993.2020.1736073

The aim of this work is to present results of both experimental and theoretical studies of 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one. In this paper, we present the chemical synthesis of 2–thioxo–3–N, (4–methylphenyl) thiazolidine 4–one followed by spectroscopy study. The applying of ¹H and ¹³C nuclear magnetic resonance (NMR), ultraviolet–visible (UV–vis) spectroscopy, performed its structural characterization. UV–vis measurements showed absorption between 250 and 350 nm. The optical gap energy is calculated using the Tauc method, which comes out to be around 3.91 eV. Density functional theory (DFT) computations were adopted for the geometry optimization of this compound and to evaluate their static polarizability (the mean polarizability (Formula presented.) and the polarizability anisotropy (Formula presented.)) and static first hyperpolarizability (the electric field–induced second harmonic generation (EFISHG) (Formula presented.) and the hyper–Rayleigh scattering (HRS) (Formula presented.)) using several functionals. These static electrical properties are studied in detail. An inverse relation between the first hyperpolarizability and the HOMO–LUMO gap has been obtained for the 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one. Based on these results, we can conclude that the synthesized molecule is considered as a good candidate for optoelectronic device applications.

Full text of DOI:10.1080/17415993.2020.1736073

Journal of Sulfur Chemistry
ISSN: 1741-5993 (Print) 1741-6000 (Online) Journal homepage: https://www.tandfonline.com/loi/gsrp20
Synthesis and DFT calculations of linear and
nonlinear optical responses of novel 2-thioxo-3-N,
(4-methylphenyl) thiazolidine-4 one
B. Baroudi, K. Argoub, D. Hadji, A.M. Benkouider, K. Toubal, A. Yahiaoui & A.
Djafri
To cite this article: B. Baroudi, K. Argoub, D. Hadji, A.M. Benkouider, K. Toubal, A. Yahiaoui
& A. Djafri (2020): Synthesis and DFT calculations of linear and nonlinear optical responses
of novel 2-thioxo-3-N,(4-methylphenyl) thiazolidine-4 one, Journal of Sulfur Chemistry, DOI:
10.1080/17415993.2020.1736073
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JOURNAL OF SULFUR CHEMISTRY
https://doi.org/10.1080/17415993.2020.1736073
Synthesis and DFT calculations of linear and nonlinear optical
responses of novel 2-thioxo-3-N,(4-methylphenyl)
thiazolidine-4 one
B. Baroudia, K. Argouba, D. Hadji b, A.M. Benkouidera, K. Toubalc, A. Yahiaouia and
A. Djafric
aLaboratory of Organic Chemistry, Macromolecular and Materials, University Mustapha Stambouli of
Mascara, Mascara, Algeria; bDepartment of Chemistry, Modeling and Calculation Methods Laboratory,
University Dr Moulay Tahar of Saida, Saida, Algeria; cFaculty of Sciences, Department of Chemistry,
Laboratory of Applied Organic Synthesis, University of Oran 1 Ahmed Ben Bella, Oran, Algeria
ABSTRACT
ARTICLE HISTORY
Received 15 October 2019
Accepted 22 February 2020
The aim of this work is to present results of both experimental
and theoretical studies of 2–thioxo–3–N, (4–methylphenyl) thia-
zolidine–4–one. In this paper, we present the chemical synthe-
sis of 2–thioxo–3–N, (4–methylphenyl) thiazolidine 4–one followed
by spectroscopy study. The applying of 1H and 13C nuclear mag-
netic resonance (NMR), ultraviolet–visible (UV–vis) spectroscopy,
performed its structural characterization. UV–vis measurements
showed absorption between 250 and 350 nm. The optical gap
energy is calculated using the Tauc method, which comes out
to be around 3.91 eV. Density functional theory (DFT) computa-
tions were adopted for the geometry optimization of this com-
pound and to evaluate their static polarizability (the mean polar-
izability ꢀαꢁ and the polarizability anisotropy ꢀα) and static first
hyperpolarizability (the electric field–induced second harmonic
generation (EFISHG) β// and the hyper–Rayleigh scattering (HRS)
KEYWORDS
Rhodanine; synthesis;
polarizabilities;
hyperpolarizabilities; NLO
β
HRS) using several functionals. These static electrical properties
are studied in detail. An inverse relation between the first hyper-
polarizability and the HOMO–LUMO gap has been obtained for
the 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one. Based on
these results, we can conclude that the synthesized molecule is con-
sidered as a good candidate for optoelectronic device applications.
CONTACT D. Hadji
hadji120780@yahoo.fr
Department of Chemistry, Modeling and Calculation Methods
Laboratory, University Dr Moulay Tahar of Saida, Saida 20000, Algeria
Supplemental data for this article can be accessed here. https://doi.org/10.1080/17415993.2020.1736073
© 2020 Informa UK Limited, trading as Taylor & Francis Group

2
B. BAROUDI ET AL.
1. Introduction
Rhodanine is a five–membered heterocyclic molecule containing a thioxo group on second
carbon and the carbonyl group on fourth carbon with thiazole nucleus. Many molecules
are designed and synthesized due to the various possibilities of structural derivatives of the
rhodanine ring [1,2]. Since the past ten years, the number of patents and scientific pub-
lications describing a plenty of the different biological applications of rhodanine–based
compounds are increasing continuously. Rhodanine has been found to possess various bio-
logical activities, such as anticancer, antidiabetic, antibacterial, antifungal, anti–infective,
pesticidal, antimycobacterial, antineoplastic, and so on [3,4]. They also show antimalarial
activities, anti–human immunodeficiency virus (HIV) and antitubercular.
Here we present a bibliographic study on rhodanine–based synthetic materials for med-
ical and physical applications. Derivatives of rhodanine can be used as anticancer. For
these applications, novel purine–pyrazole hybrids combining thiazoles, thiazolidinones
and rhodanines, were designed and tested as inhibitors. These compounds are potential
anticancer and antioxidant agents [1,5–7]. 4–thiazolidinones subtypes [3], 5–isopropylidi-
ene derivatives of 3–dimethyl–2–thio hydantoin, 3–ethyl–2–thio–2, 4–oxazolidinedione,
and 5–benzilidene–3–ethyl rhodanine are powerful against leukemic cell line in a con-
centration–dependent manner [1]. For antibacterial activity, many derivatives rhodanine
compounds are presented for a wide spectrum bactericidal agents, furanyl–substituted
rhodanine derivatives, rhodanine derivatives containing various substituents at the N3
and C5 positions, arylhydrazone derivatives bearing a rhodanine moiety, 5–aryloxypyra-
zole derivatives, pyrazole–substituted derivatives bearing rhodanine–3–fatty acid moi-
eties, rhodanine–3–acetic acid derivatives, allyl rhodanine azo dye derivatives [3] are
designed, synthesized and tested on large groups of bacteria [1]. For the antifungal activity,

JOURNAL OF SULFUR CHEMISTRY
3
rhodanine–3–acetic acid derivatives and a series of benzylidene–rhodanines acting as
antifungal agents are reported [1–8]. For the antidiabetic activity, the dispiropyrrolidine
derivatives of rhodanine which are found to exhibit attractive antidiabetic properties.
In other hand, rhodanine derivatives have several physical applications. Heterocyclic
compounds containing five membered rings with nitrogen, sulfur, and oxygen atoms have
been investigated since a long time for their important properties. Among these hete-
rocycles, there are the thiazoles, which are an important class. Recently, the push–pull
effects of thiazolidinone compounds have been receiving big attention of chemists and
physicists for their linear and nonlinear optical (NLO) properties [9–14]. Similar com-
pounds attract attention such as chalcone and derivative for optoelectronic applications
studied using combined experimental and theoretical studies [15–17]. These studies
explore the potential of these compounds and its derivatives as efficient NLO-phores.
A very simple–structured nonfullerene acceptor consisting of a bithiophene core and
octyl–substituted rhodanine can be used in the photovoltaic cells [8]. Photovoltaic prop-
erties are also investigating with simple–structured non–fullerene acceptor containing
alkoxy substituted benzothiadiazole and a rhodanine [18]. Other applications for these
kinds of compounds, rhodanine–3–acetic acid can be used in dye–sensitized solar cell as
an acceptor group [19]. Supramolecular self–assembly is one of the powerful approaches
for the development of dynamic functional soft materials. For optoelectronic properties,
supramolecular columnar self–assembly of wedge–shaped rhodanine based dyes is syn-
thesized. This material has a small π–conjugated functional organic molecule capable
of forming supramolecular columnar self–assembly [20]. These kinds of molecules can
be used as a Red emissive sensor for discriminative detection of Ag+ and Hg2+ ions in
buffer–free aqueous solutions. For this application, triarylamine rhodanine derivatives
are synthetized and tested [21]. Good thermal like our compound, chemical stability,
and the control chromophore−chromophore interactions in the solid state, can increase
the HRS and EFISH hyperpolarizability measured for unsymmetrical polymethine dyes
[22]. These factors possess the required characteristics for electro-optical applications. In
the same state, Kong et al. [23] showed that EFISH measurements reveal unprecedented
hyperpolarizabilities of twisted π-electron system. Their studies provide quantitative NLO
information on the extent of aggregation. The measurement of HRS hyperpolarizabilities
for solid-state materials show that the aggregation in the solid state undoubtedly affects
the conformation and hence the hyperpolarizability β of the material [24]. Several experi-
mental studies [25–27] of NLO properties in solid state show that the HRS measurements
in solid state facilitate the comprehension of the orientational correlation between NLO
chromophores in the film.
2. Results and discussion
2.1. Optical properties
In this work, the energy gap is calculated from the UV–vis spectrum (see Figure S1). An
absorption maximum at more than 4 eV (corresponding to the near ultraviolet region)
was observed, which highlights the π − π∗ transition between the highest occupied and
the lowest unoccupied electron band of this compound. As shown in Figure S1, the UV–vis

4
B. BAROUDI ET AL.
Figure 1. Absorption spectrum of 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one as a function
of the energy.
spectroscopy confirms that the synthesized compound has a good optical absorption with
tunable intensities and regions.
Figure 1 shows the evolution curves of the absorption coefficient α of the synthesis com-
pound as a function of the incident photon energy E. Referring to this figure; we calculated
the band gap energy (ꢀε) using a Tauc plot method [28–31] based on the linear adjust-
ment of the X–axis intercept, which comes out to be around 3.91 eV. It should be noted
that we used a quartz cell with 10 mm thick to obtain the Absorption spectrum. This calcu-
lated ꢀε value reflects the semiconductor nature of the 2–thioxo–3–N, (4–methylphenyl)
thiazolidine–4–one.
The absorption spectrum reveals that the 2–thioxo–3–N, (4–methylphenyl) thiazoli-
dine–4–one, capable of absorbing visible radiation. Therefore, it can be very suitable for
optoelectronic device applications.
2.2. Static electrical properties results
2.2.1. Computational details
The geometry of this compound has been optimized at the B3LYP functional [32] using
the 6–311 + G(d,p) basis set implemented in Gaussian 09 [33]. The optimized molecu-
lar geometry and their coordinates are showed in Figure S5 and Table S1, respectively.
The Gaussian 09 suite of programs [33] was used for all static electrical properties cal-
culations. The GaussView 5.1 program [34] was used to visualize the structure and
HOMO and LUMO orbitals. We are interested in calculating and studying theoretically
the dipole moment µ, the static polarizability α and the static first hyperpolarizability β of
the 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one. For α, we calculated the mean
polarizability ꢀαꢁ and the polarizability anisotropy ꢀα. For the static first hyperpolarizabil-
ity β, we are interested in the values of the EFISHG β// and the HRS phenomena βHRS. The
B3LYP functional is usually considered a gateway choice to predict the NLO properties of

JOURNAL OF SULFUR CHEMISTRY
5
small molecules [35]. The calculation of these static electrical properties was performed
using several DFT functionals (PBE0, B3PW91 [36], B3LYP [32], CAM–B3LYP [37], M06
[38], M05–2X and M06–2X [39]). Several theoretical studies showed that corrected XC
functionals are more reliable compared to traditional functionals to predict polarizabil-
ity and first hyperpolarizability [40–42]. For the EFISHG, β// is the central quantity,
the vector component of β projected along the dipole moment axis (multiplied by a
factor of 3/5),
ꢀ
ꢀ
1
5
μ
|μꢂi|
β//(−2ω; ω, ω) = β//
=
(β + β + β )
(1)
ijj
jij
jji
i
j
In the static limits, the component β = β = β
ijj
jij
jji
and so,
ꢀ
3
μ β
i
5 i=x,y,z |μꢂ|i
β//
=
(2)
|μꢂ| is the norm of the dipole moment
μ and β the ith components of the µ and βvectors, respectively, with:
i
i
β = βxxx + βxyy + β
x
xzz
β = βyyy + βyxx + β
y
yzz
and
β = βzzz + βzxx + β
z
zzz
All these contributions (βxxx, βxxy, βxyy, βyyy, βxxz, βxyz, βyyz, βxzz, βyzz and βzzz) can be cal-
culated using Gaussian 09 [33]. We provide in Table S2 in SI each value as taken from output
file for all eight DFT calculations.
In HRS, the depolarization ratios DR were also calculated. For a non–polarized incident
signal, and for the reason that both polarizations are detected with equal sensitivity, the
orientational average over β is
ꢁ
ꢁ
|βHRS| = βH2 RS
=
βZ2ZZ + βZ2XX
(3)
and
βZ2ZZ
βZ2XX
2ω
I
I
VV
DR =
=
(4)
2ω
HV
ꢀβZ2ZZꢁ and ꢀβZ2XXꢁ are orientational averages of the β tensor components, describing the
HRS intensities when the incident light is vertically or horizontally polarized, respec-
tively. These two invariants ꢀβZ2ZZꢁ and ꢀβZ2XXꢁ are calculated without assuming Kleinman’s

6
B. BAROUDI ET AL.
conditions and are defined as [43]:
x,y,z
x,y,z
x,y,z
x,y,z
ꢀ
ꢀ
ꢀ
ꢀ
1
7
4
35
2
35
4
35
βZ2ZZ
=
βζ2ζζ
+
βζ2ζη
+
βζζζ βζηη
+
βηζζ βζζη
ζ
ζ=η
ζ=η
ζ=η
x,y,z
x,y,z
x,y,z
x,y,z
ꢀ
ꢀ
ꢀ
ꢀ
4
35
1
35
4
105
1
105
+
+
βζζζ βηηζ
+
βη2ζζ
+
βζζηβηεε
+
βηζζ βηεε
ζ=η
ζ=η
ζ=η=ε
ζ=η=ε
x,y,z
x,y,z
x,y,z
ꢀ
ꢀ
ꢀ
4
105
2
4
+
βζζηβεεη
+
βζ2ηε
βζηεβηζε
(4)
105
105
ζ=η=ε
ζ=η=ε
ζ=η=ε
x,y,z
x,y,z
x,y,z
x,y,z
ꢀ
ꢀ
ꢀ
ꢀ
1
4
105
2
35
8
105
βX2ZZ
=
βζ2ζζ
+
βζζζ βζηη
−
βζζζ βηηζ
+
βζ2ζη
35
ζ
ζ=η
ζ=η
ζ=η
x,y,z
x,y,z
x,y,z
ꢀ
ꢀ
ꢀ
3
35
2
1
+
−
βζ2ηη
−
βζζηβηζζ
+
35
βζηηβζεε
35
ζ=η
ζ=η
ζ=η
x,y,z
x,y,z
x,y,z
ꢀ
ꢀ
ꢀ
2
105
2
2
105
βζζηβηεε
+
βζ2ηε
−
βζηεβηζε
(5)
35
ζ=η=ε
ζ=η=ε
ζ=η=ε
2.2.2. Dipole moment
The dipole moment values obtained using B3LYP/6–311 + G(d,p) level act in parallel with
the hyperpolarizability results (Table1). We can see that the dipole moment values obtained
with the M06 functional are systematically smaller than those obtained with other func-
tionals. The results show that by using hybrid functionals B3LYP, PBE0 and B3PW91, the
μ values are in the range of 1.62–1.77 D. In fact, the PBE0 functional gives the high dipole
moment value.
The variations of the dipole moment as a function of the exchange–correlation func-
tionals (B3LYP, PBE0, B3PW91, CAM–B3LYP, ωB97X–D, M06, M05–2X and M06–2X)
attain 15%. Kulinich et al. [44] showed that the dipole moment of rhodanine derivatives
increases under excitation. In this paper, we calculate dipole moment at the ground state
and not under excitation.
Table 1. Dipole moment µ, mean polarizability ꢀαꢁ, anisotropy polarizability |α|, gas phase EFISHG
β//, the HRS first hyperpolarizability βHRS and the depolarization ratios DR obtained using eight DFT
functionals at 6–311 + G(d,p) basis set.
µ
ꢀαꢁ
|α|
β//
β
tot
βHRS (DR)
B3LYP
1.62
1.64a
1.77
1.69
1.61
1.69
1.25
1.56
1.59
167.89
171.28a
173.12
166.14
164.11
163.91
167.39
163.26
163.78
75.55
–234.24
435.45
509.71a
535.42
427.73
363.72
396.63
434.44
381.06
349.76
212.56 (3.61)
212.56 (3.61)
248.17 (3.97)
206.52 (3.37)
192.61 (2.88)
200.66 (3.10)
210.87 (3.34)
190.75 (3.22)
188.00 (2.82)
PBE0
82.67
75.62
70.15
70.17
75.42
71.17
71.52
–281.34
–230.17
–208.71
–228.24
–234.27
–223.59
–204.66
B3PW91
CAM–B3LYP
ωB97X–D
M06
M05–2X
M06–2X
a[52].

JOURNAL OF SULFUR CHEMISTRY
7
2.2.3. Polarizability
The average polarizability was calculated using the polarizability components by the
formula
1
3
ꢀαꢁ = (αxx + αyy + α )
(6)
zz
and the anisotropy of polarizability by the formula:
ꢂ
1
2
|ꢀα| =
[((αxx − α )2 + (αxx − α )2 + (αyy − α )2)]
(7)
yy
zz
zz
Using several DFT functionals at the same 6–311 + G(d,p) basis set, the mean polariz-
ability values α for the 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one is shown in
Table 1. The analysis of the results in Table 1 shows that, similarly for dipole moments, the
values of the polarizability α depend on the method used. By using the B3LYP, PBE0 and
B3PW91 functionals, the α values are in the range of 166–173 a.u. The corrected func-
tionals CAM–B3LYP and ωB97X–D display α value in the range of 163–164 a.u. Not a
significant difference between the results obtained with the two functionals M05–2X and
M06–2X.
Unusual enhancement of the mean polarizability ꢀαꢁ and the anisotropy polarizability
ꢀα is shown using the Perdew–Burke–Ernzerhof (PBE0) calculation. Theoretical papers
[45,46] show the efficiency of the PBE0 functional to predict mean polarizability ꢀαꢁ and
the anisotropy polarizability ꢀα. A PBE0 calculation is more appropriate according to the
paper of Adamo et al. [45]. In addition, Sabirov et al. [46] showed that for all the stud-
ied multi–cage nanostructures, the PBE0 functional gives polarizability with high accuracy
and are in perfect agreement with the measured values. Our results show that, when passing
from the traditional functionals B3LYP, PBE0 and B3PW91 to the long–range functionals
CAM–B3LYP and ωB97X–D, small changes are observed. In the case of C60 [47], the PBE0
polarizability value is in extraordinary agreement with the experimental value using exper-
imental photoabsorption cross sections and the density–of–states technique. The authors
showed that this functional gives accurate polarizability compared to other DFT func-
tionals used in their paper and MP2 level. Other examples of the reliability of the PBE0
functional to reproduces the polarizability values like the work of Hornberger et al. [48]
and Sabirov et al. [49], the authors showed that the PBE0 method reproduces the measured
ꢀα of fullerene halogenides (C60F36 and C60F48).
2.2.4. Hyperpolarizability
It is well known that conjugated molecules generally have a much larger NLO effect than
unconjugated molecules, indicating a dominant contribution of π–delocalized electrons.
For the βHRS, the average ꢀβHRSꢁ made on the equiprobable orientations taken by a
molecule. The calculations hyperpolarizability show that the contributions along the x-
axis are the majority, also, because x-axis is the major charge transfer axis in our designed
compound. The molecule is placed in the xy-plane with the groups along the x-axis
(Figure 2).
In our compound, the theoretically calculated β values for the 2–thioxo–3–N,
(4–methylphenyl) thiazolidine–4–one (Table 1 and Figure 3) are 5.8 times larger than
the values for hyperpolarizability of urea [50]. Bureš [51] showed in their study of

8
B. BAROUDI ET AL.
Figure 2. Orientation of the studied molecular system during calculations.
Figure 3. β// (left) and βHRS (right) of the 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one deter-
mined at different levels of approximation.
structure–properties relationships in push–pull compounds that compounds with thiazol
acceptor have high first hyperpolarizability β. Indeed, the author showed that substitu-
tion of 4–nitrophenyl by the 5–nitrothiazole and 6–nitrobenzo[d]thiazole increase the
first hyperpolarizability β values from 50 to 70 esu. He noted that push–pull compounds
connected to thiazol acceptor are thermally stable (near to 300°C). In this paper, we
also confirmed that the 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one is thermally
stable.
Due to their important charge distribution and high first hyperpolarizabilities β
of this type of molecular framework, recent studies [52,53] have shown the impor-
tance of rhodanine derivatives in the synthesis and design of NLO compounds.
Anbarasan et al. [52] have shown that the total first hyperpolarizability value of the
(E)–5–benzylidine–2–thioxothiazolidine–4–one (E5BTTO) is twelve times greater than

JOURNAL OF SULFUR CHEMISTRY
9
that of urea. Their obtained total first hyperpolarizability results are in good accordance
with our results for the 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one using the
same B3LYP/6–311 + G(d,p) level of theory. Indeed, the obtained dipole moment µ and
the mean polarizability ꢀαꢁ obtained for the rhodanine derivative (E5BTTO) [52] are in
perfect accordance with our results (Table 1). The study [52] shows the importance of the
presence of rhodanine derivatives in materials for the NLO applications. If we compare the
results obtained with the different functionals, we find that are little differences between the
functionals CAM–B3LYP, M05–2X and M06–2X. The same assessment has been obtained
by Hadji and Champagne [54] in their detailed study of the HRS first hyperpolarizabil-
ity βHRS using several DFT functionals. The authors showed that the βHRS values obtained
using M05–2X and M06–2X DFT functionals at the same aug–cc–pVDZ basis set are quite
similar. In this study, the PBE0 functional contains amount 40% of HF exchange displays
the highest first hyperpolarizability β
values, whereas, the M06–2X DFT functional,
HRS
which contains amount 54% of HF exchange, gives the smallest βHRS values (Table 1 and
Figure 3).
Among the NLO applications that have been investigated for rhodanine derivatives, we
can cite the study of Svetlichnyi et al. [55]. The authors showed the suitability of rhoda-
nine derivatives for NLO applications using two–photon absorption investigations. Indeed,
the study [55] showed that the two–photon absorption cross sections of two rhodanine
derivatives are measured and equal to 115 and 125 GM, respectively. Our static first hyper-
polarizability calculations show that the β
is inversely proportional to the β// values.
HRS
The β
values of 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one is 248.17 a.u.
HRS
using M06–2X/6–311 + G(d,p) calculation, which is the lowest β
value obtained for
HRS
this rhodanine derivative, while the β// value of the same compound becomes the largest
(–204.66 a.u.) using the same calculation level (Table 1 and Figure 3).
A similar situation is found for the depolarization ratios DR. The DFT functionals used
in this work give close DR values for the same studied compound. Their DR values range
from 3 to 4 using M06–2X and PBE0 levels, respectively. These data, in combination with
the chemical topology of the 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one struc-
ture, is congruent with the representative Cs molecular point group. Indeed, in general,
the DR property covers a broad range of octupolar-dipolar characters of compounds; this
factor makes it possible to characterize the microscopic symmetry of the molecule when it
has a few elements of the non-zero hyperpolarizability tensor.
2.3. Frontier Molecular Orbitals (FMOs) and their energy gaps
This theoretical study showed that the gap|HOMO–LUMO| or (ꢀε) varied from 2.80 to
8.31 eV using PBE0 and ωB97X–D functionals (Table 2 and Figure 4), respectively, which
implies the eventual charge transfer interaction–taking place within the rhodanine deriva-
tive: The 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one studied in this work. The
low ꢀε value (2.80 eV) has been obtained using the PBE0 level at the 6–311 + G(d,p) basis
set. Good agreement has been obtained between the experimental obtained values using
the Tauc plot method [28–31] noted above (ꢀε = 3.91 eV) and their obtained using
exp
theoretical levels B3LYP, B3PW91 and the PBE0 functionals at 6–311 + G(d,p) basis set
(ꢀε
= 4.38, 2.80 and 4.74 eV), respectively. Recent theoretical study [56] of the β
PBE0
HRS

10
B. BAROUDI ET AL.
Figure 4. HOMO and LUMO orbitals of the 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one and
their ꢀε (in eV) estimated by several DFT functionals at the 6–311 + G(d,p) basis set.
and the gap|HOMO–LUMO| of heteroleptic bis–cyclometalated iridium(III) complex con-
taining 2–phenylpyridine and picolinate ligands showed that the PBE0 functional gives
similar experimental gap values compared to CAM–B3LYP and M06–2X levels. The same
assessment has been obtained in this study.
According to the FMOs illustrated in the Figure4, the electron density in HOMO is delo-
calized on the cycle carries the two sulfur atoms and the phenyl. Both functionals PBE0,
B3LYP, M05–2X and M06–2X well represent this delocalization (Figure 4). Whereas, all

JOURNAL OF SULFUR CHEMISTRY
11
Table 2. HOMO, LUMO, gap|HOMO–LUMO| and the β
6–311 + G(d,p) basis set.
obtained using eight DFT levels at the
HRS
E HOMO
E LUMO
gap|HOMO–LUMO|
β
HRS
B3LYP
PBE0
–6.14
–5.19
–6.26
–7.70
–8.29
–6.34
–7.70
–7.64
–1.76
–2.39
–1.85
–0.51
0.01
–1.52
–0.73
–0.81
4.38
2.80
4.74
7.18
8.31
4.81
6.96
6.83
3.91
212.56
248.17
206.52
192.61
200.66
210.87
190.75
188.00
B3PW91
CAM–B3LYP
ωB97X–D
M06
M05–2X
M06–2X
Exp
DFT functionals used in this paper showed that the electron density of the LUMO is local-
ized on the cycle carries the two sulfur atoms. The study showed that higher values of the
β
HRS as well as lower energy gap (ꢀε) for the 2–thioxo–3–N, (4–methylphenyl) thiazoli-
dine–4–one (Table 2). Therefore, an inverse relation between the gap|HOMO–LUMO| and
the HRS first hyperpolarizability βHRS has been obtained. The same findings were obtained
in our previous studies [54,56–58].
3. Experimental section
3.1. Synthesis of 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one
The synthesis of the title compound was performed according to Schemes 1 and 2. The
synthesis was carried out in two steps; the first is to produce dithiocarbamate salt as fol-
lows. 0.1 mole of paratoulidine (a) was introduced into 10 ml of triethylamine. After, 0.11
mole of carbon disulfide was added to form the N paramethyltoulidine triethylammonium
dithiocarbamate (b). The resulting solid was washed and dried to be used in the second
step.
The dithiocarbamate salt (b) was solubilized in 50 ml of water with magnetic stirring for
one hour at 0°C. Sodium chloroacetate was then added. The mixture is put ender mechan-
ical stirring for 15 min at 0°C. Concentrated HCl (0.1–0.2 N) was added to acidify the
medium. The reaction mixture was refluxed ender (100°C).
The precipitate was filtered off to give the title compound with a moderate yield 65%.
The melting point of this compound is 152°C.
Scheme 1. Synthesis of N paramethyltoulidine triethylammonium dithiocarbamate.

12
B. BAROUDI ET AL.
Scheme 2. Synthesis of 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one (C).
3.2. Spectroscopic data of 2–thioxo–3–N, (4–methylphenyl) thiazolidine–4–one
Electronic spectra were recorded on a spectrum instrument SP–UV 200 S spectropho-
tometer with quartz cell of 10 mm at 25°C. The 1H and 13C NMR spectra were measured
in CDCl3 and TMS with a Bruker AC–DPX–200 (300 MHz) spectrometer at 25°C. The
UV–vis analysis and NMR characterizations of the synthesized molecule are as follows
and presented in Figure S2, Figure S3, Figure S4 and Figure S5.
NMR 1H (300 MHz, CDCl3/TMS) δppm, J Hz:
2.44 (s, 3H); 4.17 (s, 2H); 7.21–7.35 (dd, 4H, AB, J = 7.75).
NMR 13C (300 MHz, CDCl3/TMS) δppm:
21.42 (CH3); 36.46 (CH2); (128.07;130.41;132.41;140.03)(C–aryl); 173.61 (C = S);
201.52 (C = O).
UV–visible λ(nm): 264 (C = C); 304 (C = S).
4. Conclusions
In this paper, we have reported synthesis of the 2–thioxo–3–N, (4–methylphenyl) thiazoli-
dine–4–one that has been characterized by means 1H and 13C NMR, UV–vis spectroscopy.
The synthesis was carried out in two steps; the first is to produce dithiocarbamate then the
second for obtaining the final product. The optical gap energy is calculated using the Tauc
method, which comes out to be around 3.91 eV.
On the other hand, a theoretical calculation of the NLO properties of the 2–thioxo–3–N,
(4–methylphenyl) thiazolidine–4–one was performed theoretically by using DFT com-
putations. For this we are using eight functionals at the 6–311+ G(d,p) basis set. The
high values of the obtained HRS first hyperpolarizabilities β
show the suitability of
HRS
this rhodanine in the NLO field, where the β values for 2–thioxo–3–N, (4–methylphenyl)
thiazolidine–4–one is 5.8 times greater than that of urea using PBE0/6–311 + G(d,p) cal-
culation. The PBE0 functional gives the highest HRS first hyperpolarizability βHRS, and
the lowest gap|HOMO − LUMO| compared to other functionals used in this study. An
inverse relationship between the two properties (ꢀε and βHRS) was obtained. The B3LYP
functional performed better to estimate the gap|HOMO − LUMO|, indeed, a small differ-
ence was obtained between the calculated values (ꢀεB3LYP) and that of the experiment.
To enhance the first hyperpolarizability for this compound, a strategy consists in inves-
tigating the push–pull configuration, which is a rudimentary principle to design efficient
NLO-phores, as this was carried out by Muhammad et al. [59–61] in the case of chalcone

JOURNAL OF SULFUR CHEMISTRY
13
derivatives and dinitrophenol derivatives [62]. These derivatives have already been synthe-
sized and the structure-NLO property relationships were studied using DFT and TD–DFT
functionals. Basing on the experimental and the theoretical study, we conclude that this
compound appears to be potentially good candidates for application in the field of the solar
cells and nonlinear optics.
Acknowledgements
DH thanks Pr B Champagne of Namur University in Belgium for his help on HRS hyperpolarizability
calculation.
Disclosure statement
No potential conflict of interest was reported by the author(s).
ORCID
D. Hadji http://orcid.org/0000-0003-3058-0627
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