Growth dynamics and molecular structural analysis of Dimethylketo thiosemicarbazone single crystals for frequency conversion applications - Optical and thermal characterization

Article abstract of DOI:10.1016/j.molstruc.2021.130463

New organic Schiff base of Dimethylketo thiosemicarbazone (DMKT) was synthesized by condensation process and grown by solvent slow evaporation method in methanol solution. The grown crystal was subjected to a single crystal and powder X-ray diffraction study and to identify that the material crystallized into a triclinic crystal system with a P-1 noncentrosymmetric space group. The X-Ray data reveals that the crystalline network cohesion of this compound. The FT-IR and FT Raman spectral analysis show the vibration behavior of chemical bonds in the grown material. Its optical behavior was examined by UV–VIS spectrum and the DMKT crystal was found to have transparency in the region between 350 nm and 1100 nm. The luminescent emission of the grown material was identified from the fluorescence spectrum. Improvement in the second harmonic generation efficiency of the grown material was studied by the Kurtz and Perry powder method and it shows 26.7 mV of green light emission. The thermal stability and melting point of DMKT were confirmed by various thermal analyses.

Full text of DOI:10.1016/j.molstruc.2021.130463

Journal of Molecular Structure 1239 (2021) 130463
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstr
Growth dynamics and molecular structural analysis of Dimethylketo
thiosemicarbazone single crystals for frequency conversion
applications - Optical and thermal characterization
a,c
b,∗
R. Sakunthaladevi , L. Jothi
a
Department of Physics, Trinity College for Women, Namakkal-637002, Tamil Nadu, India
Department of Physics, N.K.R. Government Arts College for Women, Namakkal-637001, Tamil Nadu, India
Periyar University, Palkalai Nagar, Salem-636011, India
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
New organic Schiff base of Dimethylketo thiosemicarbazone (DMKT) was synthesized by condensation
process and grown by solvent slow evaporation method in methanol solution. The grown crystal was
subjected to a single crystal and powder X-ray diffraction study and to identify that the material crystal-
lized into a triclinic crystal system with a P-1 noncentrosymmetric space group. The X-Ray data reveals
that the crystalline network cohesion of this compound. The FT-IR and FT Raman spectral analysis show
the vibration behavior of chemical bonds in the grown material. Its optical behavior was examined by
UV–VIS spectrum and the DMKT crystal was found to have transparency in the region between 350 nm
and 1100 nm. The luminescent emission of the grown material was identified from the fluorescence spec-
trum. Improvement in the second harmonic generation efficiency of the grown material was studied by
the Kurtz and Perry powder method and it shows 26.7 mV of green light emission. The thermal stability
and melting point of DMKT were confirmed by various thermal analyses.
Received 28 February 2021
Revised 2 April 2021
Accepted 7 April 2021
Available online 13 April 2021
Keywords:
Schiff base
X-ray diffraction
Linear and Nonlinear optical studies
Simultaneous thermal studies
©
2021 Elsevier B.V. All rights reserved.
1
. Introduction
group [6]. Which have attracted considerable attention due to their
wide-ranging applications, like liquid crystals, organic dyes, cata-
lysts, and as intermediates for many bioactive molecules [7]. In
nonplanar Schiff base compounds exhibit photochromism and such
materials realized in various areas such as radiation control, ra-
diation measurement, optical computers, and display systems [8].
Some of these types of materials have been already reported by
many researchers [9-13]. At the same time condensation of aro-
matic aldehydes or ketones with thiosemicarbazides extend the
electron delocalization along with the azomethine and donor sites
in the ketonic part which offers much more coordination possi-
bilities for the thiosemicarbazone. This coordinating capability of
thiosemicarbazides is attributed to the unlimited delocalization of
electron density over the N-H, C-S, N-H systems, which is im-
proved by substitution at the position of N. In this various inter-
molecular or interionic hydrogen bonding have played an impor-
tant role in constructing supramolecular structures and involves in
the generation of noncentrosymmetric structures [14]. The linkage
between ketones and thiosemicarbazides yield a keto thiosemicar-
bazones prompted us to design new Schiff bases [15]. Thiosemicar-
bazones have received considerable attention because of their un-
predictable bonding modes, promising biological implications and
structural diversity [16].
Organic molecular materials have many potential applications
in photonics, integrated optics, and the diode laser frequency dou-
bles. Direct frequency doubling of semiconductor diode lasers of-
fers a variety of applications like optical storage, optical chemistry,
underwater communication, etc. The important properties of such
applications were its transparency, second harmonic generation ef-
ficiency, phase matching, etc. [1-2]. One of the advantages in work-
ing with organic materials is they have large structural diversity
so it was altering their structure, to increase their NLO properties
of its pure one [3]. This will increase their desired nonlinear op-
tical properties of the material like second harmonic generation,
optical rectification, and parametric amplification [4]. The second
harmonic generation is a phenomenon produced by the second-
order nonlinearities in a material when it is exposed to high in-
tensity and monochromatic light sources [5]. Organic Schiff bases
were synthesized by condensation between a primary amine and
an aldehyde or ketone to form an azomethine or imine (-C=N-)
group. This is due to the presence of a very high polar carbonyl
∗
Corresponding author.
E-mail address: jothilakshmanan@gmail.com (L. Jothi).
https://doi.org/10.1016/j.molstruc.2021.130463
0
022-2860/© 2021 Elsevier B.V. All rights reserved.

R. Sakunthaladevi and L. Jothi
Journal of Molecular Structure 1239 (2021) 130463
Fig 1. Reaction mechanism of Dimethylketo thiosemicarbazone.
Table 1
Crystal data and structure refinement parameters for Dimethylketo thiosemicar-
bazone.
Empirical formula
Formula weight
C4H9N3S
131.20
Temperature
296 (2) K
Wavelength
0.71073 A
Crystal system, space group
Unit cell dimensions
Triclinic, P -1
a = 6.229(4) A, alpha 85.20(4) deg
b = 7.8557(2)A, beta = 68.329(2) deg
c = 7.987(5)A, gamma = 70.23 deg
3
Volume
341.4(3) A
Z
2
Calculated density
Absorption coefficient
F(000)
1.271 Mg/m3
−
1
0.376 mm
140
Crystal size
0.200 × 0.180 × 0.150 mm
3.744 to 36.429 deg
-10<=h<=10, -13<=k<=13, -13<=l<=13
21,273
Theta range for data collection
Limiting indices
Fig. 2. As grown single crystal of Dimethylketo thiosemicarbazone.
Reflections collected
Unique Reflections
Completeness to theta = 25.00
Absorption correction
Max. and min. transmission
Refinement method
3308 [R (int) = 0.064]
98.5 %
Semi-empirical from equivalents
0.7471 and 0.6053
Full – matrix least-squares on F2
This prompted our study into the synthesis, growth and charac-
terization of dimethylketo thiosemicarbazone (DMKT) single crys-
tals for the first time. The three-dimensional X-ray crystal struc-
ture, optical, mechanical and thermal perspectives of these crystals
are also presented in this paper. These techniques are very useful
for characterizing and identifying various properties of the grown
new DMKT material.
Data / restraints / parameters
Goodness-of-fit on F2
3308 / 4/ 86
1.086
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0523, wR2 = 0.1485
R1 = 0.0717, wR2 = 0.1711
0.34(8)
Extinction coefficient
−
3
Largest diff. peak and hole
0.402 and -0.389 e.A
2. Experimental procedure
2
.1. Material synthesis
carbon-oxygen double bond gets broken and the carbonyl group
undergoes addition reactions, with the loss of a water molecule.
This reaction is known as addition-elimination or condensation
[17]. Based on this the Schiff base of dimethylketo thiosemicar-
bazone was synthesized.
The starting compounds are purchased from Sigma Aldrich with
9% purity. Thiosemicarbazide salt was dissolved in methanol solu-
9
tion and start condensing after few minutes, dimethyl ketone was
added drop by drop in an appropriate ratio. The chemical reaction
was shown in Fig. 1. A supersaturated solution of Dimethylketo
thiosemicarbazone was obtained for the continuous condensation
of 8 hrs with a temperature of 80 °C.
Their physicochemical properties were investigated by using
various structural, optical and thermal analyses. The selected crys-
tal was employed in Bruker D8 VENTURE SC-X ray diffractometer
and radiated by a source of Mo(Kα) radiation with the help of an
attached accurate goniometer. The PHOTON 100 CMOS detector is
optimized for the detection of radiations by single crystal X-ray
diffraction. Accurate unit cell parameters were refined by the se-
lection of 3308 unique reflections out of 21,273 total reflections.
Data collection was performed by using the APEX3 software pro-
gram and the structure refined by Full-matrix least-squares were
given in Table 1.
2
.2. Crystal growth
The supersaturated solution was filtered in a beaker by using
what mann filter paper. The beaker was kept in an undisturbed
position and allowed to solvent slow evaporation at room tem-
perature at atmospheric pressure. Within 20 days a number of
seed crystals are visible for a filtered solution in a beaker and af-
ter 55 days colourless single crystal of various dimensions is ob-
In powder XRD, a monochromatic X-ray beam was focused on
the powder sample having a diameter less than 10 μm to deter-
mine structural information in the crystal lattice. It was also used
to analyze materials identity, crystallinity, residual stress and tex-
tural features with minimum invasion [18]. Interactions of incident
X-rays with the sample atomic planes create diffracted, transmit-
ted, refracted, scattered and absorbed beams according to Bragg’s
law [19] 2dsinθ = nλ, which relates the order of diffracted beam
(n), the wavelength of the incident X-ray beam (λ) to the distance
between nearatomic planes (d-spacings) and the angle of the inci-
tained. The grown single crystal of DMKT with the dimension of
3
7
× 7 × 2 mm was shown in Fig. 2.
2
.3. Characterization Techniques
The slightly positive carbon atom in the carbonyl group of ke-
tone can be attacked by a negatively charged ion or a slightly neg-
atively charged part of a molecule in thiosemicarbazide and the
2

R. Sakunthaladevi and L. Jothi
Journal of Molecular Structure 1239 (2021) 130463
Fig. 3. Schematic diagram of Dimethylketo thiosemicarbazone single crystal.
Table 2
dence (θ). Changeover of diffracted patterns into d-spacings allows
recognition of the unknown sample and was identified by com-
paring the diffracted pattern beams with many reference patterns
stored in the JCPDS library or XRD textbooks [20-24]. Using Rigaku
Ultima III X-ray diffractometer and the diffracted beam were de-
tected.
4
Atomic coordinates (x 10 ) and equivalent isotropic
displacement parameters ( A˚ 2 x 10 ) for Dimethylketo
3
thiosemicarbazone.
x
y
z
U(eq)
S
1865(1)
3073(3)
5396(3)
7539(4)
4200(2)
3802(2)
6456(2)
5756(2)
4432(1)
1368(2)
1640(2)
962(3)
2144(1)
7911(2)
6699(2)
7297(3)
2925(2)
4579(2)
1962(2)
5173(2)
49(1)
57(1)
43(1)
66(1)
38(1)
44(1)
50(1)
45(1)
C(1)
C(2)
C(3)
C(5)
N(1)
N(2)
N(3)
A Perkin Elmer-Paragon Fourier Transform Infrared Spectrome-
ter was used to record the infrared vibrational spectrum of DMKT.
The spectrum was recorded by the KBr pellet technique in the
3681(2)
3013(2)
3659(2)
2386(2)
−1
− 1
ranges from 4000 cm
spectrum of DMKT was recorded in the region of 4000–500 cm
to 400 cm . Fourier Transform Raman
−
1
by using Bruker RFS 27 FT-Raman spectrometer equipped with
FRA-106 model.
Internal optical transmittance of DMKT material was recorded
using Perkin Elmer Lambda 35 UV–VIS spectrometer in the wave-
length range of 200–1100 nm. The fluorescence emission spectrum
of DMKT was recorded by using Perkin Elmer LS 45 fluorome-
ter. Among the various NLO effect, the frequency doubling or sec-
ond harmonic generation ability of a material can be analyzed by
using the Kurtz Perry powder method. In this method the crys-
tal has been powdered with the uniform particle size and tightly
packed in a microcapillary tube of a uniform bore. The tube was
mounted in the path of the Q-switched Nd: YAG laser beam emit-
ting a wavelength of 1064 nm, with a power of 1.2 mJ [25]. The
output was collected in a monochromator with an IR blocking fil-
ter. A photomultiplier was used to detect the out coming green
light and the optical signal was converted into voltage output at
the cathode ray oscilloscope.
Table 3
Hydrogen bonds for Dimethylketo thiosemicarbazone [A and deg.].
D-H...A
d(D-H)
d(H...A)
d(D...A)
<(DHA)
C(1)-H(1B)...S#1
C(3)-H(3C)...S#2
N(1)-H(1)...S#1
N(2)-H(2A)...S#3
N(2)-H(2B)...S#4
0.96
2.79
3.683(3)
3.838(2)
3.550(2)
3.674(3)
3.436(2)
155.8
0.96
2.91
162.7
0.916(16)
0.848(14)
0.861(14)
2.754(19)
3.015(19)
2.582(15)
145.9(19)
136.2(17)
171.4(19)
3
. Result and Discussion
3
.1. X-Ray Diffraction Studies
Suitable
crystals
of
DMKT
with
dimension
The melting point and mass change due to temperature was an-
alyzed by using various thermal analysis. The differential scanning
calorimetry (DSC) measurement for DMKT was carried out by us-
ing a sample of 15 g with a NETZSCH DSC 204 F1 PHOENIX ther-
mal analyzer and to get simultaneous TG-DSC and TG-DTG thermal
traces by NETZSCH STA 449 F3 Jupiter thermal analyzer. Schematic
diagram of Dimethylketo thiosemicarbazone single crystal is shown
in Fig. 3
3
0
.2 × 0.18 × 0.15 mm were selected for single crystal X-ray
diffraction analysis. From the result, DMKT crystallized into the
triclinic system with P1 space group. The atomic coordinates and
isotropic displacement parameters of DMKT was given in Table 2.
In the unit cell, the packing of molecules was stabilized by the
interaction of hydrogen bonding between them and the observed
interactions are given in Table 3 and the interactions were C1-
H1B...S , C -H ...S , N -H ...S , N -H ...S , and N -H ...S . The
1
3
C3
2
1
1
1
2
A2
3
2
B2
4
3

R. Sakunthaladevi and L. Jothi
Journal of Molecular Structure 1239 (2021) 130463
Fig. 4. ORTEP plot of Dimethylketo thiosemicarbazone with 50% probability.
Table 4
Bond lengths [A] and Bond angles [deg] for Dimethylketo thiosemi-
carbazone.
S-C(5)
1.6975(16)
1.489(2)
0.9600
C(2)-C(1)-H(1A)
109.5
C(1)-C(2)
C(1)-H(1A)
C(1)-H(1B)
C(1)-H(1C)
C(2)-N(3)
C(2)-C(3)
C(3)-H(3A)
C(3)-H(3B)
C(3)-H(3C)
C(5)-N(2)
C(5)-N(1)
N(1)-N(3)
N(1)-H(1)
N(2)-H(2A)
N(2)-H(2B)
C(2)-C(1)-H(1B)
H(1A)-C(1)-H(1B)
C(2)-C(1)-H(1C)
H(1A)-C(1)-H(1C)
H(1B)-C(1)-H(1C)
N(3)-C(2)-C(1)
N(3)-C(2)-C(3)
C(1)-C(2)-C(3)
C(2)-C(3)-H(3A)
C(2)-C(3)-H(3B)
H(3A)-C(3)-H(3B)
C(2)-C(3)-H(3C)
H(3A)-C(3)-H(3C)
H(3B)-C(3)-H(3C)
N(2)-C(5)-N(1)
N(2)-C(5)-S
109.5
109.5
0.9600
109.5
0.9600
109.5
1.2833(19)
1.498(2)
0.9600
109.5
126.35(14)
116.40(15)
117.24(14)
109.5
0.9600
0.9600
1.3247(19)
1.3462(18)
1.3897(18)
0.916(16)
0.848(14)
0.861(14)
109.5
109.5
109.5
109.5
109.5
117.22(13)
123.26(11)
119.47(11)
118.17(12)
119.3(15)
121.2(15)
119.9(14)
119.4(14)
120.1(17)
117.54(13)
N(1)-C(5)-S
C(5)-N(1)-N(3)
C(5)-N(1)-H(1)
N(3)-N(1)-H(1)
C(5)-N(2)-H(2A)
C(5)-N(2)-H(2B)
H(2A)-N(2)-H(2B)
C(2)-N(3)-N(1)
Fig. 5. Unit cell diagram of Dimethylketo thiosemicarbazone.
pound with displacement ellipsoids were drawn 50% probability
and shown in Fig. 4.
selected bond lengths and bond angles were given in Table 4.
Some thiosemicarbazone derivatives, the N-N bond lengths were
The Unit cell and hydrogen bonding diagram of the grown
˚
˚
˚
reported in the range 1.3782–1.389 A [26], 1.3866 A [27], 1.3894 A
DMKT crystal along the b-axis were given in Fig. 5 and 6 respec-
˚
˚
[
28], 1.3966 A [29].
tively. The bond length between S-C5 is 1.6975 A and the bond an-
For the title compound, the N-N bond length was 1.3897 which
gles are C -N -N = 118.17°, N -C -S = 123.26°, N -C -S = 119.47°
5
1
3
2
5
1
5
is due to an N-N single bond and N=N double bond. The bond at
.2833 shows the typical double bond between C =N and a single
and N -C -N = 117.22°.
2
5
1
1
Anisotropic displacement parameters of the form -2π2
2
3
˚
˚
[h2a U11 +...+2hka b U12] were given in Table 5. Different
hydrogen coordinates with their corresponding isotropic displace-
ment parameters were given in Table 6. The various tensional
∗2
∗ ∗
bond of C -N , C -N was obtained at 1.3247 A and 1.3462 A re-
5
2
5
1
spectively. This is smaller than the normal C-N single bond length
˚
of about 1.48 A this is due to the effect of resonance in the
molecule [30]. The ORTEP plot of the molecules in the title com-
angles C -N -N -C
2
=
-175.39°, N(2)-C(5)-N(1)-N(3)
=
1.3(2),
5
1
3
4

R. Sakunthaladevi and L. Jothi
Journal of Molecular Structure 1239 (2021) 130463
Fig. 6. Hydrogen bonding diagram of Dimethylketo thiosemicarbazone.
Table 5
Table 7
Anisotropic displacement parameters (A2 x 10 ) for Dimethylketo
3
Torsion angles [degree] found in
Dimethylketo thiosemicarbazone.
thiosemicarbazone.
Atom
U11
U22
U33
U23
U13
U12
N(2)-C(5)-N(1)-N(3)
S-C(5)-N(1)-N(3)
1.3(2)
179.14(10)
0.3(2)
S
48(1)
65(1)
56(1)
76(1)
43(1)
43(1)
45(1)
49(1)
63(1)
60(1)
39(1)
72(1)
37(1)
52(1)
62(1)
49(1)
37(1)
44(1)
38(1)
66(1)
30(1)
32(1)
38(1)
40(1)
16(1)
18(1)
6(1)
-17(1)
-20(1)
-23(1)
-46(1)
-11(1)
-12(1)
-13(1)
-19(1)
-19(1)
-22(1)
-15(1)
-26(1)
-12(1)
-14(1)
-19(1)
-17(1)
C(1)-C(2)-N(3)-N(1)
C(3)-C(2)-N(3)-N(1)
C(5)-N(1)-N(3)-C(2)
C(1)
C(2)
C(3)
C(5)
N(1)
N(2)
N(3)
179.46(14)
-175.39(13)
19(1)
6(1)
12(1)
16(1)
10(1)
the powder X ray diffraction pattern. The sharp and well-defined
Bragg’s peaks confirmed the high crystallinity of the grown crystals
and some low-intensity peaks also present. Powder X-ray diffrac-
tion pattern of the grown DMKT crystals was shown in Fig. 7.
Pure thiosemicarbazone shows sharp single diffraction peak at
Table 6
4
Hydrogen coordinates (× 10 ) and isotropic displacement
parameters A˚ 2x10 ).
3
17.25° and 28.21° [30] but in DMKT spectrum shows a prominent
Atom
x
y
z
U(eq)
peaks at 13.01°, 16.85° and 27.58°. The powder X-ray diffraction
pattern of DMKT showed triplet in between 24° to 25° but in the
pure compound only one peak was obtained at 24.6°. These little
bit shift of peaks was due to the addition of dimethyl ketone to
thiosemicarbazone.
H(1A)
H(1B)
H(1C)
H(3A)
H(3B)
H(3C)
H(1)
3297
778
8966
85
1796
2520
8262
85
2628
628
7288
85
7071
434
8448
98
8857
65
6429
98
8064
1953
7400
98
2230(30)
7540(30)
6760(40)
3200(30)
3350(30)
4100(30)
5360(30)
2440(30)
910(20)
70(7)
56(6)
57(6)
3
.3. Fourier Transform Infrared Vibrational studies
H(2A)
H(2B)
From FTIR spectrum is shown in Fig 8 the peaks in the re-
gion 2950–3050 cm 1, 2935–2995 cm , 1400–1510 cm
−1
and
−
−1
1275–1425 cm 1 were vibrations of the CH2 group in asymmetric
stretching, symmetric stretching, scissoring and wagging respec-
tively [31,32]. The overlapping spectra of a methyl group (CH3)
−
S-C(5)-N(1)-N(3) = 179.14(10), C(1)-C(2)-N(3)-N(1) = 0.3(2), C(3)-
C(2)-N(3)-N(1) = 179.46(14) and C(5)-N(1)-N(3)-C(2) = -175.39(13)
were listed in Table 7. There is a difference in torsion angles of
the same bonding C-C-N-N= 0.3 and 179.46 indicates the presence
of asymmetric units in the DMKT crystal.
obtained in the region of 3000–2940 cm 1 and 2960–2310 cm
−
−1
were two C-H bonds in the methyl group are contracting and one
C-H bond was contracting [31]. The grown compound shows these
3
.2. Powder XRD Studies
peaks at 2998 cm 1 and 2458 cm . The asymmetric and symmet-
−
−1
ric stretching vibrations of NH2 give rise to a band in the region of
The powder sample of the grown crystal was scanned over var-
3420–3330 cm 1 and in between 3150–3270 cm
−
−1
in the present
ious 2θ values from 0° to 60° at a rate of 1° per min. The d spac-
ing for each diffraction peak in the spectrum was identified from
work, it was observed at 3377 cm 1 and 3152 cm [33]. The band
− −1
−
in the region of 3450–3330 cm 1 appears due to NH stretching
5

R. Sakunthaladevi and L. Jothi
Journal of Molecular Structure 1239 (2021) 130463
Fig. 7. Powder X-ray diffraction pattern of Dimethylketo thiosemicarbazone.
Fig. 8. Fourier Transform Infrared spectrum of Dimethylketo thiosemicarbazone.
−
1
1
−1
−1
vibration wherein the DMKT compound it appears at 3377 cm
cm , 2722 cm due to symmetric stretching. From Fig. 9 the
sharp peak at 1644 cm 1 was assigned as C=N stretching mode
−
[
34].
The C=N stretching skeletal bands observed in 1650–1550 cm
−
−1
[40]. The in-plane bending of NH2 was observed at 1593 cm and
−1
−1
[
35, 36] which was 1597 cm in the spectrum of DMKT and con-
the band in 1076 cm was due to NH2 rocking. The N and H atom
firms the formation of Schiff base. The C-N stretching vibration
coupled with NH in-plane bending active in the region of 1320–
in CNH moves in the same direction as carbon atom in the amide
group appear at 1434 cm 1 and in opposite direction appear at
−
225 cm 1 [37] and was observed at 1268 cm
−
−1
and 1251 cm
−1
.
1292 cm [41]. The stretching of C=S mode was observed at 863
−1
1
−
1
−1
The out-of-plane bending of N-N was observed at 1076 cm
in
[38]. The C=S stretching vibrations
cm [42] and out-of-plane the rocking of NH was observed at 712
−
1
−1
the range of 1037–1083 cm
were observed in the range of 670–930 cm [39], and which was
cm
[43]. Table 8 gives the observed FT-IR and FT Raman bands
−1
with wavenumbers and the corresponding assignments.
obtained at 865 cm 1 for the title compound.
−
3
.5. Optical Transmission spectral analysis
3
.4. Fourier Transform Raman Vibrational studies
An optically polished crystal of 1 mm thickness was used for
recording the optical transmission spectrum of DMKT and shown
The FT Raman spectrum of a powdered sample of DMKT was
in Fig. 10. The optical absorption coefficient (α) was used to find,
recorded. The overlapping spectra of methyl group CH3 obtained
∝
in 3002 cm 1, 2938 cm due to asymmetric stretching and 2905
−
−1
Extinction coefficient K = 4
,
π
6

R. Sakunthaladevi and L. Jothi
Journal of Molecular Structure 1239 (2021) 130463
Fig. 9. Fourier Transform Raman spectrum of Dimethylketo thiosemicarbazone.
Table 8
Wave numbers and assignments of FT-IR and FT Raman bands of
Dimethylketo thiosemicarbazone.
FTIR (cm 1
−
)
FT-Raman (cm
−1
)
Spectral Assignments
3
2
-
377
998
3374
3002
2938
2905
1644
1498
1463
1434
1378
1292
1109
1082
1035
863
NH stretching
CH3 stretching
CH3 asymmetric stretching
CH3 symmetric stretching
C=N stretching
2
1
1
1
1
1
1
1
1
1
8
6
5
-
904
597
513
466
429
366
301
107
076
026
65
NH in plane bending
CH3 asymmetric stretching
CH3 in plane bending
CH3 in plane bending
CN stretching
NN rocking
NH2 rocking
NH rocking
CS stretching
34
612
NH wagging
79
-
CC in plane bending
CN in plane bending
CNH out of plane bending
CS out of plane bending
NH2, CH3 torsion
582
4
-
92
489
Fig. 10. UV – VIS Transmission spectrum of Dimethylketo thiosemicarbazone.
324
-
223
-
82
CNN out of plane bending
versely proportional to the bandgap energy [47]. From the UV–VIS
spectrum, it shows variations in transmission below 350 nm and
above 350 nm it shows 99%, which proves the optical linearity of
the DMKT crystal. The lower cut of wavelength was observed at
223 nm this is due to interband electronic transitions [48]. Using
the lower cut-off wavelength bandgap energy value was calculated
as 5.6 eV which is shown in Fig. 10. Also using a Tauc’s plot Eg
was obtained as 5.55 eV and shown in Fig. 11. The variation of
extinction coefficient K with photon energy was shown in Fig. 12
and a sharp rising between 5 to 6 eV indicates the bandgap en-
ergy present in this region. The high transmission of the grown
crystal in the entire visible region with a wide bandgap indicates
the low defect concentration in the grown material [49]. Urbach
energy was calculated from Fig. 13 and the value was 2.02 eV. The
bandgap energy and Urbach energy were important parameters for
designing devices in optical communication technology [50].
1
240
Bandgap energy Eg =
Urbach energy Eu =
(eV)and
λ
hν
log α
(eV ),
where λ is the lower cut-off wavelength of the sample and where
h is Plank’s constant [44-46]. Bandgap energy was the difference
in energy between the valence band and the conduction band
of a solid material it is simply the energy of forbidden electrons
movement in the material. Urbach energy was governed by the
structural disorder, an imperfection in stoichiometric and passi-
vation at the surface and the disorder of phonon states. It is in-
7

R. Sakunthaladevi and L. Jothi
Journal of Molecular Structure 1239 (2021) 130463
Fig. 11. Tauc’s plot of Dimethylketo thiosemicarbazone.
Fig. 14. Fluorescence emission spectrum of Dimethylketo thiosemicarbazone.
3
.6. Fluorescence spectral analysis
Fluorescence spectral analysis provides information about the
luminescent behaviors of the grown optical materials in a solid
state at room temperature. Excitation transitions of electrons from
the ground to the various excited states result in the occurrence of
various peaks in the fluorescence emission spectrum [51]. Fig. 14
shows the fluorescence spectrum of DMKT and three emission
peaks with different intensities in the wavelength range of 280–
9
00 nm were obtained. The first sharp peak appears at a wave-
length of 353 nm with high intensity, the second small peak ap-
pears at 528 nm with low intensity and the third medium peak
at 685 nm with medium intensity. From these, the grown DMKT
shows three types of emissions, emits ultraviolet color with an in-
tensity of 723 a.u and the wavelength range from 300 to 450 nm.
The green color with an intensity of 98 a.u was observed in the
range between 500 and 550 nm. Finally, red color with an inten-
sity of 266 a.u was emitted in the wavelength range from 600
to 850 nm. The properties of emission correlated with the in-
termolecular interactions which yield molecular conformation, the
supramolecular structure of fluorescent crystals and controllable
crystal engineering [52].
Fig. 12. Plot of extinction coefficient
K vs phton energy hν for Dimethylketo
thiosemicarbazone.
3
.7. Second harmonic generation efficiency studies
The nonlinear optical properties of a material are due to the
nonlinear polarization of light in the homogeneous but moderate
electric field. In this way, the number of bonds especially hydro-
gen bonding in material in solid-state may impact the NLO prop-
erties significantly [53]. Several NLO phenomena can occur when
intense light interacts with non-absorbing media, resultant in the
formation of new beams of dissimilar wavelengths [54]. In addi-
tion to identifying the materials with noncentrosymmetric crystal
structure, and used to identify the materials phase matching ca-
pacity [55]. The only noncentrosymmetric crystal structure can ex-
hibit the SHG and it was confirmed by the emission of green light.
The output of green light with voltage 26.7 mV and 22 mV were
obtained by DMKT and KDP crystals respectively. This notable fre-
quency doubling of the grown DMKT was attained due to the for-
mation of electronic sub energy band below the bandgap and pro-
moting more electron-proton interaction and hence it can be used
in laser industry [56, 57].
Fig. 13. Plot of lnα vs phton energy hν for Dimethylketo thiosemicarbazone.
8

R. Sakunthaladevi and L. Jothi
Journal of Molecular Structure 1239 (2021) 130463
Fig. 15. Differential Scanning Calorimetric trace of Dimethylketo thiosemicarbazone.
3
.8. Thermal analysis
indicates that the melting point of the grown material [62]. Now a
day simultaneous thermal analytical methods were used to record
two different parameters to temperature at the same time. The de-
velopment of TG, coupled with the derivative thermogravimetry
(DTG) and differential scanning calorimetry (DSC) was carried out
for the DMKT crystals.
Considerate the essential thermal properties of a given mate-
rial was an important part of material design and study. Thermal
analytical methods analysis changes in the physical and chemical
effects of material as a function of temperature [58]. It can pro-
vide the typical transformation temperatures of the process (qual-
ity characteristics) and derivative values proportional to the quan-
tity of the transformed material can be obtained [59]. A tool to
explore material thermal properties was large, one of these was
differential scanning calorimetry (DSC) which measures the heat
flow of a sample during heating (or cooling). It is useful for the
determination of several thermodynamic properties of a material
such as the melting and freezing temperatures, the specific heat,
the phase change, enthalpies, etc. [60]. The initial temperature at
which a transformation takes place as shown by the intersection
of the extension of the baseline and the tangent to the inflection
point.
The commercial thermal analyzer of simultaneous TG-DTG was
widely used for the mechanism of oxidation as fast also easy
to operate and relatively cheap [63]. From the simultaneous TG-
DTG curve the material decomposes immediately after the melting
point of 181 °C due to the gaseous products like N , H , H S, etc.
2
2
2
[64]. After that, the increases in mass losses occur in three steps
and shown in Fig. 16. A major weight loss of 60.01% in the first
step was obtained in the temperature range from 180 °C - 260
°C, which is due to the evaporation of the solvent and the pres-
ence of any other volatile matter. In the second step, the weight
loss of 23.482 % was obtained in the temperature range from 260
°C - 500 °C, which may be due to the decomposition of the main
groups such as NH, CS, CC, etc. In the last stage, the weight loss of
15.17 % was obtained in the temperature range from 500 °C - 750
°C, which may be due to the complete decomposition of the cross-
linkage between the two monomer units [64]. At the temperature
above 750 °C the sample fully decomposes and a residual mass of
1.32 % was obtained at 832 °C. The residue remains after all the
decomposition was due to the presence of carbon residue [65].
The simultaneous TG-DSC results can be difficult to interpret
due to the high complexity of the organic matter because a fusion,
decomposition and polymerizations can occur together with an in-
creasing temperature, resulting in the superposition of endother-
mic and exothermic effects [66].
Fig. 15 gives the DSC trace of the grown DMKT material, which
is obtained by the temperature versus difference in heat flow. The
heat flow differential was found between the test sample and the
reference cell due to the absorbed or released heat as a function
of constant heating rate and was registered as a temperature dif-
ferential ratio.
The formula for the DSC heat flow was measured as [61],
dH
dt
dT
dt
=
Cp
+ f(T, t)
dT
where CP is sample heat capacity, dt is the heating rate and f (T, t)
is heat flow at a function of time at an absolute temperature. The
first heat flow obtained at 0.6151 mW/mg with an area of 269 J/g
at temperature 181 °C, the second flow at 2.563 mW/mg with an
area of 34 J/g at temperature 222 °C and the third one were -6.704
with area 1820 J/g at temperature 561 °C. It shows an increase of
the DSC intensity in the range near 181 °C. This variation to be
related to an increase in molecular weight and stability, so which
Fig. 17 shows the simultaneous TG-DSC plot of DMKT, from the
TG trace the material starts to decompose at 181 °C and a sudden
fall of weight occurs in between 181 °C and 300 °C. After 300 °C a
gradual decrease in weight was obtained up to 710 °C and finally
reached a constant weight loss. Simultaneously in the DSC trace, an
endothermic peak was obtained at 181 °C after a sudden fall was
9

R. Sakunthaladevi and L. Jothi
Journal of Molecular Structure 1239 (2021) 130463
Fig. 16. Simultaneous TG-DTG trace of Dimethylketo thiosemicarbazone.
Fig. 17. Simultaneous TG-DSC trace of Dimethylketo thiosemicarbazone.
obtained up to 570 °C and after 600 °C again increases the peak.
From all the above studies the melting point of the grown DMKT
material was observed at 181 °C and it was lower than the one of
the parent compound thiosemicarbazone (183 °C) and higher than
the other parent compound dimethyl ketone (-94.7 °C). This con-
firms the formation and crystallization of the grown DMKT mate-
rial and up to 181 °C the material was used in NLO applications.
4. Conclusion
An organic Schiff base of Dimethylketo thiosemicarbazone
(DMKT) was synthesized by condensation process and an optically
3
good quality single crystal of dimension 7 × 7 × 2 mm was ob-
tained by a solvent slow evaporation method. The single crystal
and powder X-ray diffraction (XRD) studies of the grown DMKT
confirmed the material be owned to triclinic crystal system with
10

R. Sakunthaladevi and L. Jothi
Journal of Molecular Structure 1239 (2021) 130463
P-1 space group. The molecular structure and stoichiometry of the
DMKT were also elucidated from single crystal XRD studies. The
torsion angles of the same bonding C(1)-C(2)-N(3)-N(1) and C(3)-
C(2)-N(3)-N(1) with different values reveals the presence of asym-
metric units in the grown material. The presence of C=N bond-
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−1
ing shows the vibrational frequency band between 1550 cm
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1
650 cm 1 and which was attained by both FT-IR and FT Raman
−
spectra. The linear optical property was studied by using UV–VIS
transmission spectrum and it shows 99% transmission in the visi-
ble region. The energy gap values calculated from the lower cut-off
wavelength was 5.6 eV and from Tauc’s plot was 5.55 eV and the
value of Urbach energy was 2.02 eV. The fluorescence spectrum
shows the luminescent emission functioning of the grown mate-
rial. The Kurtz-Perry powder method indicates that the SHG effi-
ciency of the DMKT was 1.21 times more than that of KDP. The
sharp endothermic peak in DSC trace, a sudden weight loss in si-
multaneous TG-DTG trace and simultaneous TG-DSC trace all were
confirmed the grown DMKT crystal stable up to 181 °C and the
compound formed without any water molecule. The spectroscopic,
linear, nonlinear optical studies and thermal analysis showed that
the grown crystal is a potential candidate for solar cell fabrication,
fiber optic communications, laser applications and high tempera-
ture measurements.
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Declaration of Competing Interest
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The authors declare that they have no known competing finan-
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influence the work reported in this paper.
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26] W. Hernandez, J. Paz, A. Varisberg, E. Spodinc, R. Richter, Beyer v, Syn-
thesis, Characterization, and In Vitro Cytotoxic Activities of Benzaldehyde
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The authors thank Sophisticated Instrumentation center, Indian
Institute of Technology, Chennai for the support in single crystal
XRD, Thermal and FT Raman data collection, Prof. P.K. Das, Indian
Institute of Science, Bangalore for having protracted laser facili-
ties for SHG measurements and Archbishop Casimir Instrumenta-
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