Synthesis and DFT studies of the structure - NLO activity evaluation of 2-(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imidazole

Article abstract of DOI:10.1016/j.molstruc.2019.127004

Synthesis, characterisation and single crystal X-Ray studies of 2-(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imidazole are reported. Here after the compound is denoted as TSI. Small Angle X-Ray Diffraction (SXRD) showed that the crystal belonged to Monoclinic, P2₁/c group. The electronic and structural properties of TSI were investigated by DFT and TD-DFT methods. This molecule is a good candidate to be used in OLED devices because of high electron transport mobility and low λ_e value. The difference between λ_e and λ_h is smaller so that it has a better hole-electron transport balance in OLED devices. The calculated static first order hyperpolarizability β(000), showed that the material exhibited good non-linear optical behaviour and could be used for NLO devices. Fukui indices were calculated to identify the reactive sites of the title compound.

Full text of DOI:10.1016/j.molstruc.2019.127004

Journal of Molecular Structure 1199 (2020) 127004
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
Synthesis and DFT studies of the structure - NLO activity evaluation of
2
-(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imidazole
Rajeev.T. Ulahannan , V. Kannan , V. Vidya , K. Sreekumar c
a
b
,
*
b
a
Department of Physics, Pavanatma College Murickassery, Idukki District, Kerala, 685604, India
Department of Chemistry, Government College Kattappana, Idukki District, Kerala, 685508, India
Department of Applied Chemistry, Cochin University of Science and Technology, Kochi, 22, Kerala, India
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 16 May 2019
Received in revised form
Synthesis, characterisation and single crystal X-Ray studies of 2-(4-methoxyphenyl)-1,4,5-triphenyl-2,5-
dihydro-1H-imidazole are reported. Here after the compound is denoted as TSI. Small Angle X-Ray
Diffraction (SXRD) showed that the crystal belonged to Monoclinic, P2
structural properties of TSI were investigated by DFT and TD-DFT methods. This molecule is a good
candidate to be used in OLED devices because of high electron transport mobility and low value. The
difference between and is smaller so that it has a better hole-electron transport balance in OLED
devices. The calculated static first order hyperpolarizability (000), showed that the material exhibited
1
/c group. The electronic and
28 August 2019
Accepted 29 August 2019
Available online xxx
l
e
l
e
l
h
b
Keywords:
DFT calculations
Fukui function
Tetra-substituted imidazoles
X-ray sturcture
good non-linear optical behaviour and could be used for NLO devices. Fukui indices were calculated to
identify the reactive sites of the title compound.
© 2019 Elsevier B.V. All rights reserved.
1. Introduction
structure, reactivity and applications in optoelectronics and drug
designing.
Imidazoles are important raw materials for fine chemical syn-
thesis. They possess remarkable biological activity [1]. They have
been used in applications such as anticancer [2], antibacterial [3],
antiviral [4] antihypertensive [5] agents and antagonistic histamine
receptors [6]. Certain imidazole derivatives are characterised by
good electroluminescence properties (EL) [7e13] with excellent
electron transport ability [14e16]. Substituted phenanthro-
imidazoles were recently reported as flurophores in non doped
blue organic light emitting diodes [17,18]. A combined experi-
mental and theoretical study on phenanthroimidazole-
styryltriphenylamine derivatives has been reported by Thani-
kachalam et al. [19]. Imidazole derivatives were also used in solu-
tion processed organic-light emitting diode applications [20]. Some
imidazole derivatives were used as efficient red phosphorescent
OLEDs [21]. Demand for a suitable and better OLED material is still
growing; imidazole moiety having electron donating and electron
withdrawing groups will show better efficiency. A detailed inves-
tigation of the spectral properties, crystal structure and other
theoretical analysis could give important information regarding
The electronic and spectral properties of the title compound
were studied using density functional theory (DFT) at the ground
state and time dependent density functional theory (TD-DFT) at the
excited state. The optimized geometry of the molecule, absorption
spectra, electronic properties and nonlinear optical properties were
studied with a view to get vital information regarding synthesis and
design of new optical devices. The choice of a material to be used in
OLED devices is dependent on its low ionisation energy, low reor-
ganisation energy, high electron affinity and high electron carrier
mobility. Studies on these features are reported in this work.
2. Experimental details
Commercial clay used in this work was montmorillonite K10
which was purchased from Sigma-Aldrich, India and modified by
4
þ
ion exchange of Ti by wet chemical method. The modified clay
ꢀ
was activated at 200 C for 3 h prior to use. All other reagents were
purchased from Merck Ltd. India and were used as such. The
1
product obtained was characterised by, HNMR, FT-IR spectral
methods, SXRD and m.p. FT-IR spectrum was recorded by the KBr
pellet method on a JASCO FT-IR spectrometer in the range of
ꢁ
11
4
00e4000 cm . H NMR spectrum was recorded on a Bruker
*
Corresponding author.
E-mail address: kannanpvl@gmail.com (V. Kannan).
400 MHz instrument with tetramethyl silane (TMS) as internal
https://doi.org/10.1016/j.molstruc.2019.127004
022-2860/© 2019 Elsevier B.V. All rights reserved.
0

2
Rajeev.T. Ulahannan et al. / Journal of Molecular Structure 1199 (2020) 127004
standard in CDCl
3
.
3. Results and discussion
3.1. Molecular structure
2.1. Computational details
The title compound was synthesised and characterised by 1
H
NMR, FT-IR and SXRD. The results of SXRD showed that the crystal
belonged to monoclinic system of space group P2 /c. The crystal
Computational study of the compound, 2-(4-methoxyphenyl)-
,4,5-triphenyl-2,5-dihydro-1H-imidazole was carried out with
Gaussian 09 [22] program in the ground state using the B3LYP/6-
1G basis set to obtain the optimized molecular structure and
1
1
data obtained is summarised in Table .1. The bond parameters such
as bond length and bond angle were calculated theoretically and
experimental values obtained in SXRD analysis were compared.
Good agreements between experimental and theoretical values
were obtained. The results are shown in Table 2.
3
frequencies corresponding to its vibrational modes. Optimization of
molecular structure was done by Berny's optimization algorithm
using redundant internal coordinates [23]. A scaling factor of 0.9613
was used for obtaining a considerably better agreement with
experimental data; because, the DFT hybrid B3LYP method might
tend to overestimate the fundamental modes. The structure
deduced was confirmed to be of minimum energy because of the
absence of imaginary wave numbers on the calculated vibrational
spectrum. The animation option of GAUSSVIEW program gave a
visual presentation of the vibrational modes [24]. The absorption
and emission of the molecule were studied from the TD-DFT studies
on the molecule as this method was a very successful one to
compute the excited states [25,26]. The energy of neutral molecule
optimized in neutral state, energy of neutral molecule optimized in
cation state, energy of cation state optimized in neutral state and
energy of neutral molecule optimized in anion state were obtained
using the TD-DFT/B3LYP6-31G computations [27].
Experimental and optimized bond length and bond angles of the
title compound were compared. A good agreement was observed
and is given in Table 2. The root mean square deviation (RMSD)
values of bond length and bond angles were calculated using the
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ꢀ
ꢁ
n
P
2
1
calc
i
exp
i
expression, RMS ¼
ðn
ꢁ
n
Þ
. The RMSD for bond
nꢁ1
i
ꢀ
length was 0.459 Å and that for bond angle was 0.520 . Complete
results of these studies are given in the supplementary data.
Hydrogen refinements were done by keeping aliphatic methyl
3
CH hydrogen fixed and refined by difference in electron density
synthesis method and riding model is followed in phenyl ring.
Imidazoles are reported to show weak non covalent interaction.
Indole-benzene reported to favours
p-p stacking interaction [29].
Table 1
Crystal data and structure refinement for 2(4-methoxyphenyl)-1,4,5-triphenyl-2,5-
dihydro-1H-imidazole.
2
1
.2. Synthesis of 2-(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-
H-imidazole
Empirical formula
28 22 2
C H N O
Formula weight
Temperature
Wavelength
Volume
Space group
Mr ¼ 402.47
T ¼ 296 K
The title compound was synthesised by solvent free synthesis by
taking benzil (1 mmol), 4-methoxybezaldehyde (1 mmol), aniline
l
¼ 0.71073 Å
(
1 mmol), NH
4
OAc (1.3 mol %) and 0.2 g activated K10 clay catalyst.
3
V ¼ 2165.9 (4) Å
ꢀ
The mixture was stirred at 120 C [28]. The formation of the
product was monitored by thin layer chromatography. After the
completion of the reaction, hot ethanol was added to the mixture
and the insoluble catalyst was filtered off. The pure product was
obtained by column chromatography using hexane and ethyl ace-
tate (8:2 v/v) as eluent. The purified product was recrystallised
from ethanol. (Scheme 1).
P21/c
ꢁ3
ꢁ3
Crystal system Dx,g cm
Unit cell dimensions
Monoclinic, 1.234 Mgm
a ¼ 10.5906 (10) Å
b ¼ 10.3985 (8) Å
c ¼ 20.193 (2) Å
ꢀ
a
b
g
4
¼ 90
ꢀ
¼ 103.105 (4)
o
¼ 90
Z
F(000)
F(000 )
hklmax
848.0
848.38
14,13,26
0
2.3. X-ray diffraction studies
Crystal size
Reflections collected
0.25 ꢂ 0.25 ꢂ 0.20 mm
3302 reflections with I > 2s(I)
Single crystal X-ray diffraction patterns of 2-(4-methoxyphenyl)-
,4,5-triphenyl-2,5-dihydro-1H-imidazole were collected on Bruker
AXS Kappa Apex 2 CCD diffractometer. Data collection was carried
out using APEX 2 (Bruker, 2004), Cell refinement was done with
APEX 2/SAINT (Bruker, 2004) and data reduction with SAINT/XPREP
Bruker 2004). Structure was solved with SIR 92 program. Structure
was refined with SHELXL 97, Molecular graphics was plotted with
ORTEP-3 and Mercury.
Independent reflections
5155 independent reflections [Rint ¼ 0.032]
H-atom parameters constrained
Refinement on F2
1
Least-squares matrix: full
H-atom parameters constrained
2
2
ꢁ3
R[F > 2
s
(F )] ¼ 0.048
Drmax ¼ 0.17 e Å
2
ꢁ3
wR(F ) ¼ 0.157
Drmin ¼ ꢁ0.24 e Å
S ¼ 1.07
(
5155 reflections
2
0
81 parameters
restraints
CH3
O
NH
2
Ph
Ph
O
O
Clay Catalyst
N
N
+
+
+
NH OAc
4
0
OCH
3
120 C
CHO
Scheme 1. Synthesis of 2(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imidazole.

Rajeev.T. Ulahannan et al. / Journal of Molecular Structure 1199 (2020) 127004
3
Table 2
The experimental and optimized bond length (Å) and bond angles for 2(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imidazole.
Sl.No
Bond angle (
q
)
Experimental
Optimized
Bond length(A0)
Experimental
Optimized
1
2
3
4
5
6
7
8
9
C
C
C
6
2
6
C
C
C
1
1
1
C
N
N
2
121.15
119.34
119.44
120.22
119.57
120.21
119.85
120.30
119.85
119.74
120.29
119.66
120.05
119.45
119.74
120.80
119.66
120.18
120.15
120.07
C
C
N
C
C
C
C
C
C
2
C
C
1
1.3751
1.3733
1.4349
0.9300
1.3764
0.9300
1.3555
0.9300
1.3727
0.9300
1.3984
1.3981
1.4381
1.0807
1.3961
1.0814
1.3979
1.0815
1.3978
1.0814
2
2
1
6
1
2
C
1
H
2
C
2
C
2
H
2
C
3
C
C
2 1
3
3
3
4
4
C
H
2
H
H
2
C
C
2
C
C
3
3
4
5
3
3
2
C
4
C
4
C
C
3 2
H
H
H
3
C
C
3
C
C
4
C
5
1
0
4
4
3
5
H C
X-Ray crystal studies showed a weak Van der Waals interaction
between nearest molecules. Moreover imidazole-benzene favours
stretching frequency in the molecule.
p-p stacking interaction which helps the planar arrangement of
each molecule in the unit cell. Each unit cell consists of four title
molecule arranged in a regular fashion with almost all aromatic
rings falling in the same plane leading to a packed structure.
3
.4. Reorganisation energy, HEP and EEP
The reorganisation energy ( ), ionisation energy (IE) and elec-
l
tron affinity (EA) were investigated to calculate the energy barrier
for injection and transport rates of electrons and holes; as the
charge transport/injection and its balance was decisive for opto-
electronic materials. The ionisation energy (IE), electron affinity
3
.2. 1H NMR analysis of 2-(4-methoxyphenyl)-1,4,5-triphenyl-2,5-
dihydro-1H-imidazole
The title compound 2(4-methoxyphenyl)-1,4,5-triphenyl-2,5-
dihydro-1H-imidazolewas characterised by HNMR recorded in
(EA) and reorganisation energy (l) were obtained as follows;
1
I:E ¼ Eþ0 ꢁ E
0
CDCl
protons in the region
the region 3.75. Signals of protons attached to C13, C17, C20, C24
are obtained as doublets around 7.08e7.18. Singlet at 3.75 cor-
3
(99.8 atom % D). The compound contains one set of aromatic
0
d
6.75e7.60 and a set of aliphatic protons in
d
0
ꢁ
E:A ¼ E ꢁ E
0
0
d
d
responds to the signal of isolated proton attached to C25. The re-
sults are shown in Fig. 2.
The charge transfer rate K of electron or hole can be obtained
from the Marcus/Hush model [33], as:
0
ꢁ
E:A ¼ E ꢁ E
3.3. FT-IR analysis
0
0
Bands around 1486, 1440, 1367 and 1325 cmꢁ1 are ascribed to
where T is the temperature, k is the Boltzmann constant. The
charge transfer rate is dependent on reorganisation energy and
thus it is a very crucial factor in charge transfer proceses.
CeN stretching frequencies of the imidazole ring [30,31]. Bands
ꢁ1
around 3100-3000 cm
indicate aromatic CeH stretching fre-
quency of phenyl rings. CeC stretching vibrational bands are
ꢂ
ꢃ
À
Á
ꢁ1
ꢁ
ꢁ
ꢁ
0
0
0
observed around 1400-1650 cm [32]. CeC stretching vibrations
l
e
¼ E
0
ꢁ E
þ
E
ꢁ
ꢁ E
ꢁ1
of the title compound are observed around 1590 cm in the FTIR
spectrum. CeOeC stretching frequency of the title compound
¼
EEP ꢁ E:A
ꢁ1
showed a medium band around 1275-1200 cm . A characteristic
ꢁ
1
band around 3000-3100 cm
indicates the presence of CeH
b
a
Fig. 1. a) Molecular structure of 2-(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imidazole showed the atom numbering scheme. Displacement ellipsoids are shown at the 50%
probability level. b) Packing diagram of 2-(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imidazole.

4
Rajeev.T. Ulahannan et al. / Journal of Molecular Structure 1199 (2020) 127004
2
5
OCH3
2
2
2
1
2
3
2
0
2
4
1
9
2
3
2
9
26
N
3
N
0
1
4
2
8
1
7
2
7
5
6
1
6
18
1
2
7
1
3
1
5
1
1
1
4
8
1
0
9
Fig. 2. 1H NMR spectrum of 2-(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imidazole.
3
.5. Frontier molecular orbital analysis
ꢂ
ꢁ E 00 ꢃ
À
Á
þ
þ
þ
0
l
¼ E ꢁ E
þ
E
h
0
þ
Imidazoles having optimum HOMO-LUMO separation have
found wide applications in optoelectronic devices. The degree of
intermolecular charge transfer between electron donor to electron
acceptor group depends on the energy gap between HOMO and
LUMO. It also determines the molecular stability and activity. Mo-
lecular orbital topology was calculated at DFT/6-31G levels. The
frontier molecular orbitals were examined for characterising the
electronic and optical properties. Molecular topologies of HOMO-
LUMO orbitals of TSI are shown in Fig. 3. It is observed that
HOMO is located mainly over imidazole ring and methoxy groups,
whereas LUMO is located mainly on phenyl rings. The lowest un-
occupied molecular orbital (LUMO) and highest occupied molecular
¼
I:E ꢁ HEP
e
h
Here l is the reorganisation energy of electrons, l that of holes.
The electron extraction potential (EEP) is the difference in energy
between the anion optimized in the neutral state and anion opti-
mized in the anion state. The hole extraction potentials (HEP) is the
energy difference between the cation optimized at cation state and
anion optimized at anion state.
0
ꢁ
ꢁ
orbital (HOMO) were visualised; EHOMO, ELUMO and energy gap (
were calculated.
DE)
EEP ¼ E ꢁ E
ꢁ
Chemical reactivity can also be related to HOMO-LUMO energy
gap, a molecule with small energy gap is more polarisable and
highly reactive. The small HOMO-LUMO energy gap and a number
HEP ¼ Eþ ꢁ Eꢁ
þ
ꢁ
0
ꢁ
þ
0
of aromatic moiety suitable for
p- p* transition indicates that the
E ;E ,E ; E show the energy of neutral molecule optimized in
0
0
0
þ
title compound is a good electron transport material.
neutral state, energy of neutral molecule optimized in anion state,
energy of neutral molecule optimized in cation state, energy of
cation state optimized in neutral state respectively. The calculated
3.6. Electronic properties
values of
ference between
l
e
,
l
h, EEP, HEP, I.E and E.A are given in Table 3. The dif-
The absorption spectrum of the molecule was calculated using
l
e
and are very small suggesting that the pre-
l
h
the TD-DFT method. The absorption wavelength, oscillator strength
and corresponding absorption energies are listed in Table 4.
Experimental UVeVis spectrum for 2-(4-methoxyphenyl)-1,4,5-
triphenyl-2,5-dihydro-1H-imidazole showed 2 absorption bands
sent molecule has a better hole and electron transport balance.
Such a material can act as an ambipolar material [34].
Table 3
Reorganisation energy.
around 230 nm, 290 nm associated with
p- p* transition of aro-
matic ring, which may be correlated to the bands calculated at
270.33 and 284.38 with oscillatory strength 0.0051 and 0.0119;
these transitions are comparatively weak in solvents. The band
HEP
EEP
6.235 eV
0.349 eV
0.526 eV
0.414 eV
6.649 eV
ꢁ0.176 eV
l
e
around 330 nm is ascribed to p- p* transition within the C]N
l
azomethine group [35]. This may be correlated to the band calcu-
lated at 325.29 nm having high oscillator strength 0.1249. The
discrepancy between experimental and theoretical prediction
h
I.E
E.A

Rajeev.T. Ulahannan et al. / Journal of Molecular Structure 1199 (2020) 127004
5
Fig. 4. MEP plot of 2(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imidazole.
regions of negative potential are concentrated over electronegative
atoms (oxygen atom of methoxy group and nitrogen atoms of
imidazole) Fig. 4.
3.8. Fukui indices
Fig. 3. HOMO-LUMO plot of 2(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-
imidazole.
Fukui indices determine the important reactive sites. Fukui
indices indicate the tendency of the electronic density to deform at
a given position by donating or accepting electrons [38,39]. Fukui
functions on the jth atom site are defined as follows:
Table 4
Excitation energies and Oscillator strengths.
Excited states
Oscillator strength
E (eV)
l
(calculated)
þ
f
f
¼ q ðN þ 1Þ ꢁ q ðNÞ
j
j
j
106 ->107
106 ->108
106 ->109
106 ->107
106 ->108
106 ->107
106 ->109
106 ->110
105 ->107
106 ->110
106 ->111
101 ->107
101 ->110
106 ->112
f ¼ 0.1249
3.8115 eV
325.29 nm
ꢁ
¼ q ðNÞ ꢁ q ðN ꢁ 1Þ
j
j
j
f ¼ 0.0289
f ¼ 0.1369
3.8973 eV
4.1129 eV
318.13 nm
301.45 nm
h
i
0
j
f
¼ 0:5 q ðN þ 1Þ ꢁ q ðN ꢁ 1Þ
j
j
þ
Fukui function for an electrophilic attack is denoted by f ,
f ¼ 0.3623
4.3337 eV
286.09 nm
j
ꢁ
nucleophilic or free radical attack f j on the reference molecule,
f ¼ 0.0119
f ¼ 0.0051
4.3598 eV
4.5864 eV
284.38 nm
270.33 nm
respectively. In these equations, q is the atomic charge (evaluated
j
from Mulliken population analysis, electrostatic derived charge,
etc.) at the jth atomic site in the neutral (N), anionic (N þ1) or
cationic (N - 1) chemical species. The concept of generalized electro
(nucleo)- philicity has been introduced by Chattaraj et al. [40]. It
contains information about different global and local reactivity
descriptor and selectivity descriptor; the information regarding
electrophilic/nucleophilic power of a given atomic site in a mole-
could be the consequence of charge transfer valence-excited states
that might occur in the molecule. The excited states 105, 106, 107,
108 represent HOMO-1, HOMO, LUMO and LUMOþ1 respectively.
cule. A dual descriptor
which was defined as the difference between the nucleophilic and
D
f ðrÞ, was proposed by Morell et al. [41],
3.7. Molecular electrostatic potential (MEP)
electrophilic Fukui function and is given by,
The molecular electrostatic potential of a molecule gives infor-
þ
ꢁ
D
f ðrÞ ¼ f ðrÞ ꢁ f ðrÞ
mation about the electrophilic and nucleophilic reactivity sites as
well as hydrogen bonding interactions; it also offers a visual
method for the understanding of polarity of the molecule [36]. The
red represents the negative electrostatic potential region, blue
represents the positive and green represents the zero potential
regions; the other colours are intermediate such that, red ˂orange˂
yellow˂ green˂ blue gives the increasing order of electrostatic po-
tential. Negative regions are associated with electron rich regions
such as electronegative groups [37]. In the title compound, the
The site is favoured for a nucleophilic attack if
may be favoured for an electrophilic attack if
descriptors
and electrophilic attack at a particular site with their sign. That is,
they provide positive value for site prone for nucleophilic attack
and a negative value to the site prone for electrophilic attack.
Fukui functions are evaluated from Mulliken population analysis
and the results are given in graphical form in Fig. 5. The reactivity
D
f ðrÞ > 0, the site
D
f ðrÞ< 0. Thus dual
D
f ðrÞ provide a clear difference between nucleophilic

6
Rajeev.T. Ulahannan et al. / Journal of Molecular Structure 1199 (2020) 127004
Fig. 5. Graphical view of Fukui function for 2(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imidazole.
order for nucleophilic case is C28 > C15 > C21, the order of reac-
tivity of electrophilic case is C9 > C4> C15 while the order of sites
for free radical attack is C15 > C28 > C23 (Table 4 Suplementary
Data).
Appendix A. Supplementary data
Supplementary crystallographic data for this article is available
in Cambridge Crystallographic information (CCDC 1910169). It can
be obtained free of charge via http://www.ccdc.cam.ac.uk/.
3.9. Nonlinear optical properties
Acknowledgement
The static first order hyperpolarizability
was calculated.
b
(0,0,0) of the molecule
The authors thank SAIF CUSAT, Cochin India for Single Crystal
and HNMR analysis.
1
1=2
2
2
y
2
z
The static first hyperpolarizability
where
b
¼ ð x
b
þ
b
þb
Þ
References
[
[
1] Y. Ozkay, I. Iskar, Z. Incesu, A. Ge, Eur. J. Med. Chem. 45 (2010) 3320e3328.
2] F. Elahian, M. Akbari, M. Ghasemi, N. Behtoomee, M. Taheri, M. Amini, Lett.
Drug Des. Discov. 11 (2014) 840e843.
bx
by
bz
¼
¼
¼
bxxx
byyy
þ
bxyy
bxxy
þ
bxzz
byzz
[
3] D. Sharma, B. Narasimhan, P. Kumar, V. Judge, R. Narang, E. Clercq, J. Balzarini,
Eur. J. Med. Chem. 44 (2009) 2347e2353.
þ
þ
[4] (a)
R. Thomas, M. Hossain, Y. Sheena Mary, K.S. Resmi, S. Armakovi ꢀc ,
S.J. Armakovi ꢀc , A.K. Nanda, V.K. Ranjan, G. Vijayakumar, C.V. Alsenoy, J. Mol.
Struct. 1158 (173) (2018) 156e175;
bzzz
þ
bxxz
þ
byyz
(b) R.V. Shingalapur, K.M. Hosamani, R.S. Keri, Eur. J. Med. Chem. 44 (2009)
4244e4248.
The calculated field independent first hyperpolarizability of the
[5] H. Stark, A. Hüls, X. Ligneau, K. Puranda, H. Pertza, J. Arrang, J. Schwartz,
W. Schunacka, Arch. Pharm. 331 (1998) 211e218.
[6] H. Yanagisawa, Y. Amemiya, T. Kanazaki, Y. Shimoji, K. Fujimoto, Y. Kitahara,
T. Sada, M. Mizuno, M. Ikeda, S. Miyamoto, Y. Furukawa, H. KoikeJ, Med. Chem.
39 (1996) 323e338.
ꢁ
30
compound was 7.18 ꢂ 10
esu. Compared with the b value of urea
ꢁ
30
0
.13 ꢂ 10
esu, the title compound was found to be a good
candidate [42] as an NLO material due to its increased
p conjuga-
tion length which enhanced the hyperpolarizability of the
molecule.
[7] Y. Shen, J. Li, S. Chen, J. Wan, Y. Zhao, Z. Lu, M. Li, L. Yang, X. Yu, D. Chen, Z. Pan,
Chemistry 2 (2017) 11206e11210.
[8] W. Li, L. Yao, H. Liu, Z. Wang, S. Zhang, R. Xiao, H. Zhang, P. Lu, B. Yang, J. Mater.
Chem. 2 (2014) 4733e4736.
[
9] J. Tagare, D.K. Dubey, J. HueiJou, S. Vaidyanathan, Dyes Pigments 160 (2019)
4
. Conclusions
-(4-methoxyphenyl)-1,4,5-triphenyl-2,5-dihydro-1H-imid-
944e956.
[
10] J. Tagare, S. Sudheendran, S. Prabha, D.K. Dubey, R. Ashokkumar Yadav,
J. HueiJou, S. Vaidyanathan, Org. ele. 62 (2018) 419e428.
2
1
[11] S. Naka, H. Okada, H. Onnagawa, Appl. Phys. Lett. 76 (2000) 197e199.
12] D.F. O'Brien, M.A. Baldo, M.E. Thompson, S.R. Forrest, Appl. Phys. Lett. 74
(1999) 442e444.
azole was synthesised, characterised by FT-IR, H NMR and Single
Crystal X-ray analysis. Single crystal analysis showed that the
molecule belonged to monoclinic system and P2 /c space group.
1
[
[
[
13] N. Li, P. Wang, S.L. Lai, W. Liu, C.S. Lee, S.T. Lee, Z. Liu, Adv. Mater. 22 (2010)
527e530.
Each unit cell contained four molecules which were planar. Geo-
metric parameters, vibrational, electronic spectra, Fukui indices,
HOMO-LUMO of the title compound were studied on the basis of
DFT calculations at B3LYP/6-31G basis set. Nucleophilic and elec-
trophilic behaviour of specific sites in the molecule was analysed
using Fukui function. Electronic spectra showed transition bands
indicating that the molecule could be used as electron transport
material. Results showed that the title compound could be used as a
good NLO active material also. Proper designing, synthesis and
theoretical investigation of this kind of compounds can lead to the
development of suitable electron transport materials for organic
electronic devices.
14] A.P. Kulkarni, C.J. Tonzola, A. Babel, S.A. Jenekhe, Chem. Mater. 16 (23) (2004)
4556e4573.
[15] B. Wang, G. Mu, J. Tan, Z. Lei, J. Jin, L. Wang, J. Mater. Chem. C 3 (2015)
709e7719.
16] T. Shan, Z. Gao, X. Tang, X. He, Y. Gao, J. Li, X. Sun, Y. Liu, H. Liu, B. Yang, P. Lu,
7
[
Y. Ma, Dyes Pigments 142 (2017) 189e197.
[17] X. Qiu, J. Shi, X. Xu, Y. Lu, Q. Sun, S. Xue, W. Yang, Dyes Pigments 147 (2017)
e15.
18] W.C. Chen, Y. Yuan, Y. Xiong, L. Andrey, A.L. Rogach, Q.X. Tong, C.S. Lee, Appl.
6
[
Mater. Interfaces 9 (2017) 26268e26278.
[19] V. Thanikachalam, E. Sarojpurani, J. Jayabharathi, P. Jeeva, New J. Chem. 41
2017) 2443e2457.
20] S.S. Reddy, W. Cho, V.G. Sree, S.H. Jin, Dyes Pigments 134 (2016) 315e324.
21] D. Tavgeniene, G. Krucaite, U. Baranauskyte, J.Z. Wu, H.Y. Su, C.W. Huang,
C.H. Chang, S. Grigalevicius, Dyes Pigments 137 (2017) 615e621.
(
[
[

Rajeev.T. Ulahannan et al. / Journal of Molecular Structure 1199 (2020) 127004
22] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, (2002) 6930e6940.
7
[
J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson,
H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino,
G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda,
J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven,
J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers,
K.N. Kudin, V.N. Staroverov, T. Keith, R. Kobayashi, J. Normand,
K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi,
N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo,
J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi,
C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski,
G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas,
J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision B.01,
Gaussian, Inc., Wallingford CT, 2010.
[27] G. Velmurugan, B.K. Ramamoorthi, P. Venuvanalingam, Phys. Chem. Chem.
Phys. 39 (2014) 21157e21171.
[28] V. Kannan, K. Sreekumar, J Mol.catal.A Chem. 376 (2013) 34e39.
[29] S. Ray, A. Das, J.Molstruc. 1089 (2015) 146e152.
[30] H.G. Silver, J.L. Wood, Trans. Faraday Soc. 60 (1964) 5e9.
[31] R. Ramasamy, J. Appl. Spectrosc. 80 (2013) 492e498.
[32] R. Ramasamy, Arm.J.Phys. 8 (2015) 51e55.
[33] R.A. Marcus, Mod. Phys. 65 (1993) 599e610.
[34] R.G. Parr, Horizons of Quantum Chemistry, Springer, 1980, pp. 5e15.
[35] O. Tamer, N. Dege, D. Avcı, Y. Atalay, I.O. Ilhan, M. Çadır, Spectrochim. Acta
Part A Mol. Biomol. Spectrosc. 137 (2015) 1387e1396.
[36] J. Zevallos, A. Toro-Labbe, J. Chil. Chem. Soc. 48 (2003) 39e47.
[37] V. Balachandran, M. Murugan, V. Karpagam, M. Karnan, G. Ilango, Spec-
trochim. Acta, Part A 130 (2014) 367e375.
[
[
23] C. Peng, P.Y. Ayala, H.B. Schlegel, M.J. Frisch, J.Comp Chem. 17 (1996) 49e56.
24] R. Dennington, T. Keith, J. Millam, GaussView, Version 5, Semichem Inc.,
Shawnee Mission KS, 2009.
[38] K. Fukui, Science 218 (1982) 747e754.
[39] R.G. Parr, W. Yang, J. Am. Chem. Soc. 106 (1984) 4049e4050.
[40] P.K. Chattaraj, B. Maiti, U. Sarkar, J. Phys. Chem. A 107 (2003) 4973e4975.
[41] C. Morell, A. Grand, A. Toro-Labbe, J. Phys. Chem. A 109 (2005) 205e212.
[42] M. Adant, M. Dupuis, J.L. Bredas, Int. J. Quantum Chem. 56 (1995) 497e507.
[
[
25] (a) J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865e3868;
(
b) C. Adamo, V. Barone, J. Chem. Phys. 110 (1999) 6158e6170.
26] J. Autschbach, T. Ziegler, S.J.A. Van Gisbergen, E.J. Baerends, J. Chem. Phys. 116