Growth and characterisation of 2′, 3, 4, 4′, 5-Pentamethoxychalcone (PMC) – For non linear optical applications

Article abstract of DOI:10.1016/j.molstruc.2016.11.081

An organic NLO crystal, 2′, 3, 4, 4′, 5-Pentamethoxychalcone (PMC) with a dimension of 13?×?10?×?3?mm³ was grown by slow evaporation method. The cell parameters of PMC crystal was confirmed by Powder X-ray diffraction. FTIR and FTRaman spectros

Full text of DOI:10.1016/j.molstruc.2016.11.081

Journal of Molecular Structure 1133 (2017) 135e143
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
Growth and characterisation of 20, 3, 4, 40, 5-Pentamethoxychalcone
(PMC) e For non linear optical applications
,
*
J. Balaji a, S. Prabu b, P. Srinivasan a
a Department of Physics, University College of Engineering: Panruti, (A Constituent College of Anna University, Chennai), Panruti, 607 106, India
b Department of Physics, University College of Engineering: Ariyalur, (A Constituent College of Anna University Chennai), Ariyalur, 621 704, India
a r t i c l e i n f o
a b s t r a c t
An organic NLO crystal, 20, 3, 4, 40, 5-Pentamethoxychalcone (PMC) with a dimension of 13 ꢀ 10 ꢀ 3 mm3
was grown by slow evaporation method. The cell parameters of PMC crystal was confirmed by Powder X-
ray diffraction. FTIR and FTRaman spectroscopy were used for the identification of functional groups for
the various modes of vibrations. The UV cut off range has been determined by using optical absorption
study. Thermal stability of the grown crystal has been analysed by TG-DTA studies. Factor group analysis
and Dielectric studies were also carried out. Photoluminescence study was performed for PMC. The first
order hyperpolarizibility and HOMOeLUMO analysis were performed using DFT calculations using
Gaussian 03 software. Non linear optical (NLO) behaviour of PMC crystals is studied by using Kurtz &
Perry powder Technique and SHG efficiency has been found 2.02 times higher than that of KDP.
© 2016 Published by Elsevier B.V.
Article history:
Received 15 July 2016
Received in revised form
27 November 2016
Accepted 28 November 2016
Available online 1 December 2016
Keywords:
Chalcone
FTIR
FTRaman
Photo-luminescence
1. Introduction
attracted a great deal of interest due to their potential applications
in Non Linear Optics due to high second harmonic generation ef-
Nonlinear optical materials are the active elements for optical
communications and optical electronics. Among such NLO mate-
rials, organic materials are shown to be superior and have dis-
tinguishing features to their inorganic counter parts in terms of
synthesis, crystal fabrication, much faster optical nonlinearities,
tailorability of designing new crystals with high optical quality, cost
effective, processability, high damage threshold and ease of fabri-
cation into desired shapes [1,2]. The second-order nonlinear optical
property of organic compound is derived from conjugated delo-
ficiency and have high values than Urea [6]. a, b-unsaturated ke-
tones are commonly synthesized via the ClaiseneSchmidt
condensation. This reaction is catalyzed by acids and bases condi-
tion. In chalcone chromophores asymmetric electronic distribution
in either or both ground and excited states enhanced by substitu-
tion of suitable electron donor or acceptor group like OCH3, leading
to an increased optical nonlinearity [7]. Chalcone derivatives are
noticeable materials for their excellent blue light transmittance and
good crystallizability. In this paper we are reporting the Growth,
FTIR, FTRamam, Photoluminescence and dielectric studies of 20, 3,
4, 40, 5-Pentamethoxychalcone (PMC).
calized
p electrons and intermolecular interaction.
In the synthesis of many pharmaceuticals, chalcones are
important intermediates and in material fields chalcones have high
attention in potential applications such as Non-Linear Optical
(NLO), Optical Limiting, and Electrochemical sensing [3]. In recent
years, Chalcone NLO crystals and its derivatives have very high deal
of attraction to their large optical nonlinearities [4,5]. Chalcone
derivatives with a suitable electron donor and acceptor substituent
are one among the efficient organic NLO materials. The members of
2. Experimental
The 20, 3, 4, 40, 5-Pentamethoxychalcone (PMC) were prepared
by using the ClaiseneSchmidt condensation method. Commercially
available of 20, 40-dimethoxyacetophenone (Sigma-Aldrich) and 3,
4, 5-trimethoxybenzaldehyde (Sigma) have been procured and
used. Here, 0.01 mol of 20, 40-dimethoxyacetophenone was mixed
with 0.01 mol of 3, 4, 5-trimethoxybenzaldehyde in N,N-
Dimethylformamide (DMF) (20 ml) and the mixture was treated
with an aqueous solution of potassium hydroxide (2 ml, 30%). This
mixture was stirred well and kept aside for 24 h. The resulting solid
mass was collected by filtration and dried. Solubility study was
a, b-unsaturated ketones (Chalcones) and flavonid family have
* Corresponding author. Department of Physics, University College of Engineer-
ing: Panruti, Panruti, 607 106, Tamil Nadu, India.
E-mail address: sril35@gmail.com (P. Srinivasan).
http://dx.doi.org/10.1016/j.molstruc.2016.11.081
0022-2860/© 2016 Published by Elsevier B.V.

136
J. Balaji et al. / Journal of Molecular Structure 1133 (2017) 135e143
carried out and DMF is found that suitable solvent for the crystal
growth of PMC. The obtained compound was purified three to four
times by re-crystallizing in DMF. Optically clear and well defined
crystals were harvested after a span of some days with a dimension
of 13 ꢀ 10 ꢀ 3 mm3. The schematic representation of the reaction
and solubility curve of PMC is given in Fig. 1. Grown crystal and
morphology of PMC is shown in Fig. 2.
3. X-ray diffraction analysis
The grown crystals were characterized by Powder X-ray
Diffraction (XRD) analysis by using BRUKER, GERMANY (D8
Advance) X-ray diffractometer with Cu Ka radiation. The scanning
rate of sample was in the range of 10e80ꢁ. The powder X-ray
diffraction pattern of PMC is shown in Fig. 3. All intensity peaks
could be indexted and the lattice parameter values of PMC were
calculated from X-Ray Powder Diffraction data using XRDA
Fig. 2. As grown crystals and morphology of PMC
Fig. 3. Powder diffraction pattern of PMC
software. Grown crystal structure is found to be Orthorhombic
crystal structure system and it belongs to P212121 Space group. The
obtained lattice parameter values are depicted in table (1) which is
in good agreement with the literature value [8] (see Table 1).
4. Vibrational analysis of PMC
4.1. Factor group analysis of PMC
The factor group analysis was performed for the title compound
by following the procedures outlined by Rousseau et al. [9]. The
symmetry properties of crystal is determined by the factor group
analysis by studying the effect of the symmetry opterations of the
factors group on each type of atom in the unit cell [10]. The
vibrational spectral studies provide information about the charge
Fig. 1. Reaction mechanism and solubility curve of PMC Scheme.

J. Balaji et al. / Journal of Molecular Structure 1133 (2017) 135e143
137
corresponding FTRaman bands appear at 1152, 1028 cmꢂ1. These
are attributed to CeH in plane bending vibrations. Similarly the IR
bands observed between 899 and 738 cmꢂ1 are assigned to CeH
out of plane bending vibrations. The asymmetrical bending vibra-
tion involves out of plane bending of the CeH bonds. Two bending
vibrations, (symmetrical and asymmetrical) can occur within a
methyl group. The first of these, the symmetrical bending vibration,
involves the in-phae bending of the CeH bonds. The symmetrical
Table 1
Lattice parameter value of PMC.
Lattice parameter
Obtained value
Reported value (8)
a
b
c
V
7.4302(1) Å
7.9554(1) Å
29.383(1) Å
1736.867 Å3
Orthorhombic
7.3041(2) A
8.0288(3) A
29.217(1) A
1713.38 Å3
Orthorhombic
System
bending vibration occurs near 1375 ꢂc1mꢂ1
, the asymmetrical
bending vibrations occur near 1450 cm . In the present case the
FTIR bands appeared at 1458, 1417 cmꢂ1 and 1319 cmꢂ1 are
assigned to CH3 asymmetric and symmetric bending vibrations of
PMC respectively. The same bands are also observed in FTRaman.
The region below 1500 cmꢂ1 is fingerprint region. In
FTIR,1643 cmꢂ1 and in Raman at 1647 cmꢂ1 bands are due to
transfer interaction between the donor and acceptor groups and
possible vibrational modes of material. PMC crystallizes in non
centrosymmetric space group P212121 (D42) with orthorhombic
system and molecules in PMC occupies general sites of C1(4)
symmetry in the primitive cell. A single molecule of PMC has 48
atoms which gives rise to (48 ꢀ 4) 192 atoms in a unit cell. There are
576 vibrations predicted for PMC from group theoretical analysis,
which are distributed into 552 internal vibrational modes and 24
external vibrational modes such as 12 (3A þ 3B1 þ 3B2 þ 3B3) for
translational lattice modes and 12 (3A þ 3B1 þ 3B2 þ 3B3) for
librational lattice modes. The vibrations are seen to decompose into
G576 ¼ 144A þ 143B1 þ143B2 þ 143B3 apart from the three acoustic
modes B1 þ B2 þ B3. Table 2 represents the various possible vi-
brations that could be exhibited by PMC. The correlation diagram
presented in Table 3 using Fateley et al. [11].
carbonyl stretching of
a, beunsaturated carbonyl group [15].
Number of single band vibrations occur like CeO, CeC, and CeN
which act as identifying fingerprint of each organic molecule. The
characteristic band of CeO stretching vibrations appears in the
region 1000-1300 cmꢂ1. The FTIR bands 1269, 1213 and, 1193 cmꢂ1
and in Raman counterparts at 1248 and 1185 cmꢂ1 were assigned to
aromatic CeO stretch. Medium intensity vibrational bands at 3005-
2965 cmꢂ1 and 2860-2815 cmꢂ1 represent the asymmetric and
symmetric stretching vibrations of CH3 which ascertain the pres-
ence of methoxy group attached with aromatic compound. Vibra-
tional bands observed in FTIR at 2936 and 2835 cmꢂ1, in FTRaman
at 2940 and 2844 cmꢂ1 are assigned to asymmetric and symmetric
stretching vibrational mode of CH3 respectively for PMC.
4.2. FTIR and FTRaman analysis of PMC
The FTIR spectrum of PMC was recorded at room temperature in
the region 400-4000 cmꢂ1 by SHIMADZU FTIR spectrometer using
KBr pellet technique. FTRaman spectrum was recorded in the re-
gion 4000-400 cmꢂ1 by a Bruker RFS 100/s instrument at room
temperature. FTIR and FTRaman Spectrum for the titled compound
are shown in Fig. 4 and 5 respectively. The assigned vibrational
frequencies of functional groups present in the grown crystal are
shown in Table 4.
The hydrogen bonding plays a vital role in NLO activity of a
crystal. The fundamental role of hydrogen bonding will be different
depending on whether the hydrogen bond is intramolecular or
intermolecular and in the latter case on the specific extent and
more of interaction. Inter - molecular hydrogen bonding increases
as the concentration of the solute in solution increases and addi-
tional bands start to appear at lower frequencies near 3550-
3200 cmꢂ1 at the expense of the free hydroxyl band [12]. Based on
these facts the FTIR bands at 3456, 3219 and 3166 cmꢂ1 are
assigned to OeH stretching vibrations. In FTIR spectra, CeH
stretching vibrational bands are assigned around 3000e3100 cmꢂ1
[13]. The CeH bending frequencies are expected to arise at 1298,
1178, 1170 and 1035 cmꢂ1 (in-plane hydrogen bending) and 1016,
985, 849 and 671 cmꢂ1 (out-of-plane hydrogen bending) of ben-
zene. These bands are generally weak in Raman spectra [14]. Based
on this the FTIR bands observed at 1124 and 1020 cmꢂ1 and its
5. NMR analysis
The 1H NMR spectrum of PMC was recorded with a Bruker
AVANCE III NMR spectrometer operating at 500 MHz using CDCl3 as
a solvent for reconfirm the presence of functional groups. The 1H
NMR spectra is shown in Fig. 6. The signals were assigned based on
integral and chemical shift values. In the 1H NMR spectrum, the
signal centered at 3.889 ppm corresponds to fifteen protons is
assigned to the five of methoxyl groups of PMC. The aromatic
methine protons H-30, H-50 and H-60of dimethoxyl phenyl moiety of
Table 3
Correlation scheme of PMC.
Site Symmetry C1
Factor group symmetry D2
Activity
Raman
IR
axx
axy
axz
ayz
,
ayy
,
azz
e
Z
Y
X
Table 2
Factor group analysis of PMC.
Factor group symmetry
Site symmetry
Total vibrations
Internal mode
C
C
20 H22 O6 compound
External mode
H
O
Total mode
Optical mode
Acoustic mode
A
B1
B2
B3
138
138
138
138
552
3T,3R
3T,3R
3T,3R
3T,3R
24
60
60
60
60
240
66
66
66
66
18
18
18
18
72
144
144
144
144
576
144
143
143
143
573
e
1
1
1
3
Total
264

138
J. Balaji et al. / Journal of Molecular Structure 1133 (2017) 135e143
Fig. 4. FTIR spectrum of PMC.
Fig. 5. FTRAMAN spectrum of PMC.
PMC is resonated as a three doublets centered at 7.737 ppm,
7.574 ppm and 7.377 ppm respectively. The doublet of doublet and a
doublet signals appear at 6.574 ppm and 6.509 ppm are attributed
to the aromatic methine protons of H-2 and H-6 respectively in
trimethoxyl phenyl moiety of PMC. The signal at 6.825 ppm be
assigned to two motion protons of H-7 and H-8 in the chalcone
moiety of PMC. Thus the molecular structure of PMC material is
confirmed from the results of 1H NMR spectrum of PMC.
6. UVevisible spectrum analysis of PMC
The absorption of UV and visible light transit the electrons in the
s
and
p orbitals from the ground state to a higher energy state and
provide essential data about the structure of molecule. The optical

J. Balaji et al. / Journal of Molecular Structure 1133 (2017) 135e143
139
Table 4
FTIR and FTRAMAN assignments of PMC.
Frequency (cmꢂ1
FTIR
)
Vibrational band Assignments
FTRAMAN
3456,3219,3166
3089,3047
2936
2835
1643
e
OeH stretching
CeH stretching
CH3 asymmetric stretching
CH3 symmetric stretching
C]O stretching
e
2940
2844
1647
1602,1500
1458,1417
1319
1269,1213
1194
1577,1501
1451,1423
1353,1313
1248,1185
1185
C]C stretching
CH3 asymmetric bending
CH3 symmetric bending
CeO stretching
CeC stretching
1124,1020
899,819,775,738
Between 678 and 426
1152,1028
e
CeH in plane bending
CeH out of plane bending
CeCeC out of plane bending
e
spectrum for the grown crystal was recorded using Lab India
UV1300 UVeVis spectrophotometer in the wavelength range from
200 nm to 1100 nm. The absorption cut off wavelength of this
Fig. 7. Absorbance spectrum of PMC.
crystal is 437 nm which is due to the n-
p* transition. The presence
of n- * transition is owing to the charge transfer in the chalcone
p
moiety and may due to excitation of aromatic ring and the presence
of C]O group [16]. PMC crystal has wide transparent in visible and
near IR spectral region. A good optical transmittance is highly
substantial for an NLO crystal. The absorbance and transmittance
spectrum of PMC is shown in Fig. 7 and 8 respectively.
7. Thermal analysis
The Thermogravimetric analysis of PMC is carried out by using
NETZSCH Thermal analysis system between 30ꢁ C to 500ꢁ C at a
heating rate of 10ꢁ Cminꢂ1 in nitrogen atmosphere. The thermal
Fig. 6. 1H NMR spectrum of PMC.

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J. Balaji et al. / Journal of Molecular Structure 1133 (2017) 135e143
8. Dielectric study
Good quality samples of PMC crystals were polished on a soft
tissue paper with fine grade alumina powder (0.1 mm) dispersed in
a mixture of methanol and Dimethyl Sulfoxide and the sample was
electroded on either side with silver paste (air drying) to make it
behave like a parallel plate capacitor. A HIOKI (model 3535) LCR
meter was used to measure capacitance, DC conductivity of the
sample as a function of frequency and temperature (in the range
40e100 ꢁC). A small rectangular furnace of 20 ꢀ 20 ꢀ 20 cm3 di-
mensions whose temperature was controlled by a Eurotherm
controller (0.1 ꢁC) was used to house the sample. Sample thickness
of about 1 mm was used for the dielectric property analysis. The
temperature and frequency dependence of dielectric property
studies of grown crystals can reveal useful information about
structural changes, defect behaviour, and transport phenomena
[17].
The dielectric constant (εr) and dielectric loss (tan
calculated by using from the relations (1) & (2).
d) were
Fig. 8. Transmittance spectrum of PMC.
Ct
Dielectric constant εr ¼
εoA
(1)
(2)
stability of PMC is analysed by Theremogravimetric (TG) and dif-
ferential thermal analysis (DTA). The curves indicate the relation-
ship between temperature change and weight loss of the sample. It
is observed that the pyrolysis process of PMC includes two stages of
weight loss. The initial stage of weight loss starts from 81 ꢁC.
Endothermic peak at 81 ꢁC that lead off material to melt corre-
sponds to the melting point. Melting point of the sample is also
verified by direct melting point measurement apparatus. The first
stage may be due to the solvent volatilization and sample dehy-
dration. The second stage is attributed to the total degradation of
the PMC from 342 ꢁC. Fig. 9 shows both TG and DTA curves recorded
for PMC against temperature from ambient to 500 ꢁC.
Dielectric loss tan
d
¼ Dεr
where is εo the permittivity of free space, t is the thickness of the
sample, and A is the area of cross section of the sample and D is
dissipation factor. Fig. 10 and 11 show that variation of dielectric
constant and dielectric loss of PMC with frequency respectively.
The large values of dielectric constant at low frequency of PMC is
contributed by all four polarization namely, electronic, ionic,
dipolar and space charge polarization [18]. Space charge polariza-
tion is generally an active preponderant at lower frequencies and
high temperatures and predicts the perfection of the crystals. When
the electric charge carriers cannot follow the alternation of the ac
Fig. 9. TG/DTA spectrum of PMC.

J. Balaji et al. / Journal of Molecular Structure 1133 (2017) 135e143
141
Fig. 12. Variation of conductivity with frequency of PMC.
Fig. 10. Variation of dielectric constant with frequency of PMC.
dielectric field, εr the dielectric constant and tand is the dissipation
factor. Conductivity of PMC has high value at higher frequency in a
given temperature and found that AC conductivity increases with
increase of temperature. This increase in conductivity could be due
to a reduction in the space charge polarization at higher fre-
quencies [20]. The conductivity results from the interplay between
the drift mobility and the carrier concentration. If the conduction
occurs by hopping of carriers with a mobility reflecting the hopping
rate and modifications in the drift mobility and carrier concentra-
tion. The defect concentration increases exponentially with tem-
perature and consequently the electrical conduction also increases.
Variation of conductivity with frequency of PMC is shown in Fig. 12.
electric field and applied beyond a certain critical frequency [19],
the dielectric constant decreases with increasing frequency and
remains constant.
Energy dissipation in a dielectric material measured by dielec-
tric loss is generally attributed to the polarization of the charge or
the dipole. At all temperature dielectric loss of PMC has maximum
value at higher frequency and behaves quite similarly related to fast
dipolar relaxation. The variation of the dielectric parameter with
frequency is known as the dispersion of the dielectric material, the
most important property of the compound.
The AC conductivity is calculated by using the value of dielectric
constant and dielectric loss.
9. Photoluminescence (PL) studies
Photoluminescence spectroscopy is a non-destructive method
of probing the purity and electronic structure of materials [21] and
provides the necessary information of different responsible and
available energy states for radiative recombination. The PL spec-
trum of PMC crystal is carried out using Varian and Cary Spec-
trofluorometer. Photoluminescence (PL) spectrum of PMC crystal
sac ¼ 2
p
f ε0εr tan
d
(3)
where εo ¼ 8.854 ꢀ 10ꢂ12 Fmꢂ1, f the frequency of the applied
Fig. 11. Variation of dielectric loss with frequency of PMC.
Fig. 13. Photoluminescence spectrum of PMC crystal.

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J. Balaji et al. / Journal of Molecular Structure 1133 (2017) 135e143
Table 5
Hyperpolarizability of PMC.
molecular orbital (HOMO-LUMO) separation, which is the result of
the end-capping electron-donor groups to the efficient electron-
acceptor groups through conjugated path [22]. Both the highest
occupied molecular orbital and lowest unoccupied molecular
orbital are the main orbitals which take part in chemical stability.
The HOMO represents the ability to donate an electron, LUMO as an
electro acceptor represents the ability to obtain an electron. The
Energy difference between HOMO and LUMO orbital is called as
energy gap which is an important stability for structures and
p
bxxx
bxxy
bxyy
byyy
bxxz
bxyz
byyz
bxzz
byzz
bzzz
ꢂ620.91
ꢂ529.72
ꢂ79.44
14.46
24.40
ꢂ41.82
28.07
ꢂ68.14
8.11
calculated as HOMO energy
¼
ꢂ6.2311 eV; LUMO
60.24
energy ¼ 5.2542 eV; HOMO-LUMO energy gap ¼ 11.48 eV. First
order hyperpolarizability is a third rank tensor which can be
described by a 3 ꢀ 3 ꢀ 3 tensor. Based on Kleinman symmetry
components of the 3D matrix can be reduced to 10 components.
The calculated first order hyperpolarizability of the compound are
given in Table 5. All the calculations were carried out by the density
functional triple parameter hybrid model DFT/B3LYP using
GAUSSIAN 98W. The B3LYP/6-31G (d, P) basis set has been
employed. Domination of the first order hyperpolarizability rep-
resents the maximum charge transfer on direction compared to
others. The Second order non linearity of the compound depends
b
b
(total)
(total)
927.62 (a.u)
8.01411E-30 (e.s.u)
was recorded using the excitation wavelength 232 nm and the
emission spectrum was recorded between 400 and 650 nm. PL
spectrum of PMC is shown in Fig. 13. The spectrum shows a broad
peak nearly at 480 nm. An intense broad emission band appeared
in the range 460e480 nm which could be due to the presence of
aromatic functional group with low energy p-p
* transition, owing
to the emission of blue radiation. Hence the photoluminescence
studies confirm the suitability of PMC for blue fluorescence
emission.
mainly on the high value of b. Highest unoccupied molecular orbital
and lowest occupied molecular orbital of PMC are shown in Fig. 14.
The molecular hyperpolarizability increases with decrease of
HOMO-LUMO energy gap value of the compound.
10. HOMO-LUMO analysis
Molecular orbital (HOMO and LUMO) and their properties such
as energy are very useful for predicting the most reactive position
11. SHG analysis
in
p
electron systems and also explain several types of reaction in
Essential requisite for the second harmonic generation property
in crystalline materials is the non-centrosymmetric nature. The
nature of the crystal packing, local crystal-field effects and
conjugated system. The conjugated molecules are characterized by
a small highest occupied molecular orbital - lowest unoccupied
Fig. 14. HOMO-LUMO plot of PMC.

J. Balaji et al. / Journal of Molecular Structure 1133 (2017) 135e143
143
intermolecular interactions (such as hydrogen bonds) highly in-
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12. Conclusions
Well defined and good quality of PMC crystals has been grown
by slow evaporation method with dimension of 13 ꢀ 10 ꢀ 3 mm3.
Powder X-ray diffraction has confirmed the lattice parameter of the
crystal and it is found that crystals belong to orthorhombic system
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by the compound was calculated using factor group analysis. FTIR
and FTRaman spectroscopy ascertain the presence of various
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