Journal of Molecular Structure 1157 (2018) 536e550

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Design of geometry, synthesis, spectroscopic (FT-IR, UV/Vis, excited

state, polarization) and anisotropy (thermal conductivity and
electrical) properties of new synthesized derivatives of (E,E)-
azomethines in colored stretched poly (vinyl alcohol) matrix
Siyamak Shahab a, b, c, **, Masoome Sheikhi d, *, Liudmila Filippovich a, b, Evgenij Dikusar a,
Hooriye Yahyaei e, Rakesh Kumar f, Mehrnoosh Khaleghian g
a
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, 13 Surganov Str, Minsk, 220072, Belarus
b
Institute of Chemistry of New Materials, National Academy of Sciences of Belarus, 36 Skarina Str., Minsk, 220141, Belarus
c
Belarussian State University, ISEI BSU Minsk, Belarus
d
Young Researchers and Elite Club, Gorgan Branch, Islamic Azad University, Gorgan, Iran
e
Department of Chemistry, Zanjan Branch, Islamic Azad University, Zanjan, Iran
f
Department of Chemistry, DAV University, Jalandhar, 144012, Punjab, India
g
Department of Chemistry, Islamshahr Branch, Islamic Azad University, Islamshahr, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In the present work, the molecular structures of two new azomethine dyes:
Received 29 April 2017
Received in revised form
24 December 2017
Accepted 26 December 2017
Available online 28 December 2017

Keywords:
Azomethine dye
DFT calculation
UV/Vis spectrum
Polarizing film
Anisotropy of thermal and electrical
conductivity

have been predicted and investigated using Density Functional Theory (DFT) in dimethylformamide
(DMF). The geometries of the azomethine dyes were optimized by B3LYP/6-31þG* level of theory. The
electronic spectra of these azomethine dyes in a DMF solvent was carried out by using TD-B3LYP/6-
31þG* method. After quantum-chemical calculations two new azomethine dyes for optoelectronic ap-
plications were synthesized. FT-IR spectra of the title compounds are recorded and discussed. The

* Corresponding author. Young Researchers and Elite Club, Gorgan Branch, Is-
lamic Azad University, Gorgan, Iran.
** Corresponding author. Institute of Physical Organic Chemistry, National Acad-
emy of Sciences of Belarus, 13 Surganov Str., Minsk, 220072, Belarus.
E-mail addresses: siyamak.shahab@yahoo.com (S. Shahab), m.sheikhi2@gmail.
com (M. Sheikhi), luda1977@list.ru (L. Filippovich), dikusar@ifoch.bas-net.by
(E. Dikusar), Hooriye_yahyaei@yahoo.com (H. Yahyaei), rinkumeister@gmail.com
(R. Kumar), Mehr_khaleghian@yahoo.com (M. Khaleghian).

https://doi.org/10.1016/j.molstruc.2017.12.094
0022-2860/© 2017 Elsevier B.V. All rights reserved.
 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550 537

computed absorption spectral data of the azomethine dyes are in good agreement with the experimental
data, thus allowing an assignment of the UV/Vis spectra. On the basis of polyvinyl alcohol (PVA) and the
new synthesized azomethine dyes polarizing films for visible region of spectrum were developed. The
main optical parameters of the polarizing PVA-films (Transmittance, Polarization Efficiency and Dichroic
Ratio) have been measured and discussed. Anisotropy of thermal and electrical conductivity of the PVA-
films have been studied and explained.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
One of the most important organic dyes are azo compounds
containing nitrogen as the azo (eN]Ne) group. Azomethine is
functional group N-based 1,3-dipoles containing of an iminium ion
connected to a carbanion. These compounds used in 1,3-dipolar
cycloaddition reactions to form 5-membered heterocycles, con-
sisting pyrrolidines and pyrrolines [1,2]. Azomethine are one of the
largest and most diverse combinations of synthetic organic dyes are
being used today [3,4]. Azo compounds are extremely important
and are moderately strong and chemically stable and colorants and
broadly utilized substances in the textile, paper, coloring agents for
foods and cosmetics industries [5e7]. Azo groups were reported to
establish a variety of biological activities containing antibacterial,
antifungal, pesticidal, antiviral and anti-inflammatory activities
[1,2,8]. In addition, azomethines are used in photoluminescence
materials [9], optical materials and devices [8], organic light-
emitting diodes [10], photovoltaic cells [11] and polarizing films
[1,2,8]. Also, such kind of chemical chromohore is very promising
for the laser induced nonlinear optics [12]. In this regard Azome-
thines serve as main analytical tools by gathering a highly chro-
mophoric label, the concentration of which is easily determined by
spectrofluorimetric methods. Computational chemistry is the
application of computer simulation to predict or interpret the
chemical reactivity [13e15]. Theoretical quantum chemistry
methods is an important area in determining the mechanisms of
chemical reactions [16], especially catalysis [17], structural deter-
mination of organic compounds [18], prediction of spectroscopic
data such as 1H NMR and 13C NMR chemical shifts [19], IR, UV/Vis,
properties calculation of organic molecules [20]. Time-Dependent
Density Functional Theory (TD-DFT) is used for predicting the ab-
sorption spectra of the compounds [20e22]. We have previously
investigated the molecular geometry optimization and absorption
bands in UV/Vis spectrum of various compounds by DFT and TD-
DFT methods and it has concluded that experimental data are in
excellent agreement with theoretical results [22,23]. In this
research, we report the results of DFT calculations to investigate
absorption spectrum, UV/Vis, FT-IR, HOMO LUMO, FMO, MEP, NBO
of two new azomethine derivatives such as PA-100 and PA-101. In
this work, FT-IR spectra data and UV/Vis computations of new
synthesized azomethines in the ground state were calculated by
using density functional theory (DFT).
2. Computational methods
In this work, the quantum chemical calculations have per-
formed and optimized compounds PA-100 and PA-101 using the
Density Functional Theory (DFT) method with 6-31þG* basis sets
by the Gaussian 09 W program package [24] on a Pentium IV/
4.28 GHz personal computer. We were also used from the Time
Dependent Density Functional Theory (TD-DFT) for calculation of
the electronic transitions of the title compounds. The Polarized
Continuum Model (PCM) [22] was used for calculations of solvent
effect. Theoretical absorption spectrum of the structures in a
solvent DMF was calculated using the TD-DFT method. The theo-
retical FT-IR spectrum of the optimized structures PA-100 and PA-
101 was calculated by B3LYP/6-31þG* methods. The electronic
properties such as EHOMO, ELUMO, HOMO-LUMO energy gap, dipole
moment (mD), point group and natural charge of the title structures
were calculated [25]. The optimized molecular structures, HOMO
and LUMO surfaces were visualized using GaussView 05 program
[26]. Also the electronic structure of the compound PA-101 were
studied by using Natural Bond Orbital (NBO) analysis [25] using
B3LYP/6-31þG* level of energy in order to understand hyper-
conjugative interactions and charge delocalization.
2.1. Optimized structure of the compounds PA-100, PA-101
DFT calculations for the new compounds PA-100 and PA-101
were carried out by B3LYP/6-31þG* methods. The optimized mo-
lecular structures of the title compounds are shown in Fig. 1. All the
quantum chemical calculations were performed using the Gaussian
09 software package and GaussView 05 visualization programs on a
Pentium IV/4.02 GHz personal computer. The IEFPCM (Integral
Equation Formalism PCM) coupled to UAKS radii is a method that
was used to calculate the solvent (DMF) effect. The Integral Equa-
tion Formalism PCM, by Cances, Mennucci and Tomasi is the most
popular PCM version. It employs a molecule shaped cavity
composed of spheres centered on the nuclei, while the reaction
field is modeled by placing charges on the cavity surface. The
selected experimental and calculated geometrical parameters such
as bond lengths (Å) and bond angles ( ) of the structures PA-100
and PA-101 have been obtained by B3LYP/6-31þG* method and
they are listed in Tables 1 and 2. From Tables 1 and 2, it has been
observed that the calculated parameters show good approximation
and can be used as a foundation to calculate the other parameters
for the title compounds.
2.2. Electronic structure and excited states of the compounds PA-
100, PA-101
We used the Time-dependent density functional theory (TD-
DFT) for predicting the absorption spectra of the compounds PA-
100 and PA-101. The theoretical absorption spectra of the opti-
mized compounds were calculated in solvent DMF using the
TDB3LYP/6-31þG* method. 20 excited states considered for the
calculation equations that were performed using the IEFPCM (In-
tegral Equation Formalism PCM) method coupled to UAKS radii.
The exact amount of the maximum absorption wavelength (lmax) to
the title compounds is obtained using the TD-DFT method.
20 excited states and wavelengths of electronic absorption
spectrum of the compound PA-100 is shown in Table 3. As can be
seen from Table 3, the strong peak at lmax ¼ 395 nm and the
oscillator strength f ¼ 0.96 is due to charge transfer of electron into
the excited state S0/S2 with wave function including six configu-
rations [(H-5/L), (H-2/L), (H-1/L), (H-1/Lþ1), (H/L),
(H/Lþ1)]. The transition from HOMO-1 to LUMO (H-1/L) is main
responsible for formation maximum wavelength at 395 nm
538 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550

Fig. 1. Optimized molecular structures of the compounds PA-100 and PA-101 calculated by B3LYP/6-31þG* level of energy.

Table 1
Selected optimized geometrical parameters Bond lengths (Å) and Bond angles ( ) of the compound PA-100 calculated by B3LYP/6-31þG* method.

Bond lengths (Å) Bond angles ( )

Parameter Experimental Calculated Parameter Experimental Calculated

C(1)eC(2) 1.410 1.395 C(1)eC(2)eC(3) 1120.11 119.98

C(1)eC(6) 1.402 1.410 C(1)eC(6)eC(5) 118.22 118.19
C(2)eC(3) 1.403 1.398 C(2)eC(3)eC(4) 119.92 119.65
C(3)eC(4) 1.411 1.401 C(4)eC(5)eC(6) 120.47 120.68
C(4)eC(5) 1.397 1.393 C(5)eC(6)eC(7) 123.41 123.23
C(5)eC(6) 1.407 1.411 C(6)eC(7)eC(8) 127.73 127.61
C(6)eC(7) 1.459 1.462 C(7)eC(8)eC(9) 121.69 121.60
C(7)eC(8) 1.361 1.356 C(8)eC(9)eN(10) 121.89 121.72
C(8)eC(9) 1.453 1.444 C(9)eN(10)eC(11) 120.31 120.18
C(9)eN(10) 1.300 1.292 C(11)eC(12)eC(13) 120.71 120.68
N(10)eC(11) 1.399 1.402 C(11)eC(16)eC(15) 120.91 120.83
C(11)eC(12) 1.401 1.408 C(12)eC(13)eC(14) 120.33 120.29
C(12)eC(13) 1.392 1.390 C(13)eC(14)eC(15) 119.56 119.43
C(13)eC(14) 1.401 1.404 C(14)eC(15)eC(16) 120.12 120.06
C(14)eC(15) 1.412 1.405 C(13)eC(14)eN(17) 116.52 116.40
C(15)eC(16) 1.387 1.391 C(15)eC(14)eN(17) 123.70 123.63
C(16)eC(11) 1.410 1.411 C(14)eN(17)eN(18) 124.79 124.52
C(14)eN(17) 1.436 1.430 N(17)eN(18)eC(19) 124.11 124.07
N(17)eN(18) 1.250 1.253 C(19)eC(20)eC(21) 119.93 119.87
N(18)eC(19) 1.439 1.436 C(20)eC(21)eC(22) 120.31 120.14
C(19)eC(20) 1.403 1.402 C(21)eC(22)eC(23) 119.82 119.77
C(20)eC(21) 1.400 1.396 C(22)eC(23)eC(24) 120.51 120.47
C(21)eC(22) 1.385 1.399 N(18)eC(19)eC(20) 116.90 116.83
C(22)eC(23) 1.397 1.400 N(18)eC(19)eC(24) 122.58 122.40
C(23)eC(24) 1.391 1.395 N(10)eC(9)eH(32) 121.63 121.56
C(24)eC(19) 1.401 1.404

(Table 3). The electronic transitions in organic compounds and
some other compounds can be determined by ultravioletevisible
spectroscopy, provided that transitions in the ultraviolet (UV). An
electron from a p-bonding orbital to an antibonding p orbital* is
denoted as a p/p* transition. Auxochromes with free electron
pairs denoted as n have their own transitions, as do aromatic pi
bond transitions. Sections of molecules which can undergo such
detectable electron transitions can be referred to as chromophores
since such transitions absorb electromagnetic radiation (light).
Fig. 2 shows shape molecular orbitals participants at
lmax ¼ 395 nm. According to Fig. 2, the electron density of HOMO-1
is mainly focused on imine group (eC]Ne), double bonds (eC]
Ce), azo group (eN]Ne) and two phenyl rings and the electron
density of LUMO is mainly focused on double bonds (eC]Ce) of
non-phenyl rings, imine group (eC]Ne) and azo group (eN]Ne).
Therefore the electronic transition from the HOMO-1 to LUMO is
due to the contribution of pi (p) bonds. The other important excited
state is S0/S1 at 504 nm (f ¼ 0.32) with four configurations for
 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550 539

Table 2
Selected optimized geometrical parameters Bond lengths (Å) and Bond angles ( ) of the compound PA-101 calculated by B3LYP/6-31þG* method

Bond lengths (Å) Bond angles ( )

Parameter Experimental Calculated Parameter Experimental Calculated

C(1)eC(2) 1.391 1.387 C(1)eC(2)eC(3) 120.03 119.97

C(1)eC(6) 1.421 1.413 C(1)eC(6)eC(5) 117.47 117.42
C(2)eC(3) 1.407 1.405 C(2)eC(3)eC(4) 119.63 119.57
C(3)eC(4) 1.410 1.406 C(4)eC(5)eC(6) 121.73 121.67
C(4)eC(5) 1.400 1.392 C(5)eC(6)eC(7) 123.48 123.59
C(5)eC(6) 1.403 1.409 C(6)eC(7)eC(8) 127.84 127.93
C(6)eC(7) 1.459 1.456 C(7)eC(8)eC(9) 121.62 121.50
C(7)eC(8) 1.360 1.359 C(8)eC(9)eN(10) 122.11 122.00
C(8)eC(9) 1.447 1.441 C(9)eN(10)eC(11) 120.20 120.18
C(9)eN(10) 1.300 1.294 C(11)eC(12)eC(13) 120.91 120.87
N(10)eC(11) 1.402 1.399 C(11)eC(16)eC(15) 120.60 120.57
C(11)eC(12) 1.411 1.416 C(12)eC(13)eC(14) 120.14 120.16
C(12)eC(13) 1.380 1.387 C(13)eC(14)eC(15) 119.26 119.19
C(13)eC(14) 1.411 1.409 C(14)eC(15)eC(16) 120.52 120.61
C(14)eC(15) 1.413 1.406 C(13)eC(14)eN(17) 125.20 125.10
C(15)eC(16) 1.396 1.390 C(15)eC(14)eN(17) 115.71 115.69
C(16)eC(11) 1.403 1.408 C(14)eN(17)eN(18) 115.92 115.81
C(14)eN(17) 1.420 1.411 N(17)eN(18)eC(19) 115.50 115.43
N(17)eN(18) 1.263 1.261 C(19)eC(20)eC(21) 119.71 119.63
N(18)eC(19) 1.415 1.418 C(20)eC(21)eC(22) 120.68 120.51
C(19)eC(20) 1.411 1.408 C(21)eC(22)eC(23) 120.00 119.91
C(20)eC(21) 1.397 1.392 C(22)eC(23)eC(24) 120.01 119.90
C(21)eC(22) 1.400 1.403 N(18)eC(19)eC(20) 124.93 124.88
C(22)eC(23) 1.401 1.398 N(18)eC(19)eC(24) 115.44 115.35
C(23)eC(24) 1.402 1.396 N(10)eC(9)eH(33) 121.41 121.33
C(24)eC(19) 1.398 1.404 C(3)eO(25)e(C26) 119.00 118.93
C(3)eO(25) 1.352 1.360 C(2)eC(3)eO(25) 116.12 116.02
O(25)eC(26) 1.436 1.432 C(4)eC(3)eO(25) 124.46 124.40

Table 3
Electronic absorption spectrum of the compound PA-100 calculated by TDB3LYP/6-31þG*.

Excited Wavelength Excitation Configurations Composition (corresponding transition orbitals) Oscillator

State (nm) Energy (eV) Strength (f)

S1 504 2.45 0.23(H-1/L) þ 0.15(H-1/Lþ1) þ 0.59(H/L) þ 0.19(H/Lþ1) 0.32

S2 392 3.16 0.10(H-5/L)  0.20(H-2/L) þ 0.41(H-1/L) þ 0.11(H-1/Lþ1)  0.36(H/L) þ 0.32(H/Lþ1) 0.96
S3 372 3.33  0.43(H-1/L) þ 0.54(H/Lþ1) 0.00
S4 327 3.78 0.25(H-3/L) þ 0.57(H-2/L) þ 0.19(H-1/L) þ 0.16(H/Lþ1) 0.09
S5 318 3.88  0.12(H-7/L) þ 0.56(H-3/L)  0.27(H-2/L) þ 0.12(H-2/Lþ1)  0.16(H-1/Lþ1) 0.00
S6 310 3.99  0.10(H-6/L) þ 0.62(H-5/L) þ 0.16(H-5/Lþ1) þ 0.10(H-3/L)  0.10(H/Lþ1) 0.03
S7 307 4.02  0.21(H-6/L)  0.15(H-5/L) þ 0.16(H-3/L)  0.11(H-2/Lþ1)  0.16(H-1/L) þ 0.55(H- 0.21
1/Lþ1)  0.10(H/Lþ1) þ 0.11(H/Lþ2)
S8 300 4.13 0.63(H-4/L)  0.20(H-4/Lþ1) 0.02
S9 299 4.14 0.53(H-6/L) þ 0.12(H-6/Lþ1) þ 0.12(H-2/Lþ1) þ 0.29(H- 0.10
1/Lþ1)  0.19(H/Lþ2)  0.11(H/Lþ3)  0.10(H/Lþ4)
S10 287 4.30  0.32(H-7/L) þ 0.11(H-6/Lþ1)  0.12(H-6/L)  0.16(H-5/Lþ1)  0.13(H-3/L)  0.10(H- 0.11
3/Lþ1) þ 0.47(H-2/Lþ1) þ 0.10(H-1/Lþ1)
S11 277 4.46 0.13(H-7/L) þ 0.17(H-6/L)  0.13(H-3/L) þ 0.13(H-1/Lþ2) þ 0.59(H/Lþ2) 0.07
S12 272 4.54 0.31(H-7/L)  0.17(H-6/L)  0.11(H-6/Lþ1) þ 0.42(H-3/Lþ1) þ 0.31(H- 0.01
2/Lþ1)  0.10(H/Lþ2)  0.14(H/Lþ3)  0.11(H/Lþ4)
S13 269 4.60  0.35(H-7/L)  0.12(H-5/Lþ1)  0.10(H-3/L) þ 0.47(H-3/Lþ1)  0.25(H- 0.02
2/Lþ1) þ 0.10(H/Lþ2) þ 0.10(H/Lþ3)
S14 264 4.68 0.26(H-4/L) þ 0.49(H-4/Lþ1) þ 0.12(H-1/Lþ3)  0.29(H/Lþ3) þ 0.19(H/Lþ4) 0.00
S15 260 4.75  0.19(H-7/L)  0.18(H-5/L) þ 0.41(H-5/Lþ1)  0.29(H/Lþ4) þ 0.33(H/Lþ5) 0.02
S16 258 4.79 0.13(H-6/L) þ 0.40(H-5/Lþ1) þ 0.11(H-4/Lþ1) þ 0.13(H-3/Lþ1) þ 0.11(H- 0.02
2/Lþ1) þ 0.28(H/Lþ3) þ 0.35(H/Lþ4)  0.14(H/Lþ5)
S17 255 4.86 0.19(H-7/L) þ 0.10(H-7/Lþ1) - 0.27(H-6/Lþ1)  0.21(H-5/Lþ1) þ 0.22(H-4/Lþ1)  0.11(H- 0.02
3/Lþ1) þ 0.37(H/Lþ3)  0.10(H/Lþ4) þ 0.27(H/Lþ5)
S18 252 4.91  0.15(H-6/L) þ 0.56(H-6/Lþ1) þ 0.19(H-4/Lþ1) þ 0.27(H/Lþ3) 0.01
S19 247 5.00 0.10(H-7/Lþ1) þ 0.14(H-6/Lþ1)  0.22 (H-4/Lþ1) þ 0.37(H/Lþ4) þ 0.42(H/Lþ5)  0.19(H/Lþ6) 0.04
S20 245 5.05  0.10(H-2/Lþ2) þ 0.65 (H-1/Lþ2)  0.13(H/Lþ2) 0.00
*
H-HOMO, L-LUMO.

electronic excitations [(H-1/L), (H-1/Lþ1), (H/L), (H/Lþ1)].
The other excited states of the title compound have very small in-
tensity (f z 0) that is nearly forbidden by orbital symmetry con-
siderations (Table 3).
The calculated electronic absorption spectrum (UV/Vis) of the
compound PA-100 in solvent (DMF) and experimental spectrum at
concentration 3.54$104 M/l and in solvent (DMF) is observed in
Fig. 3a and b. The calculated and experimental magnitudes of
maximum wavelength (lmax) are 392 nm (f ¼ 0.96, Fig. 3a) and
406 nm (Fig. 3b), respectively. As can be seen, the experimental
540 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550
Fig. 2. Form of the MO involved in formation of absorption spectrum of the compound PA-100 at lmax ¼ 392 nm calculated by B3LYP/6-31þG* method.
value of wavelength is in excellent agreement with the theoretical
value.
According to results of theoretical calculations in Table 4, the
strong absorption peak in electronic absorption spectrum of the
compound PA-101 at lmax ¼ 400 nm is observed at oscillator
strength f ¼ 1.76. The wavelength maximum is due to charge
transfer of electron into the excited state S0/S2, which it is a wave
function including one configuration for electron excitations
[(HOMO/LUMO)]. The form molecular orbitals participants at
excited state S0/S2 is shown in Fig. 4. According to Fig. 4, the
electron density of HOMO is mainly focused on azo group (eN]
Ne) and the electron density of LUMO is mainly focused on imine
group (eC]Ne), double bonds (eC]Ce), azo group (eN]Ne) and
two phenyl rings. Therefore the electronic transitions from HOMO
to LUMO are due to the contribution of pi (p) bonds. The other
excited states of the title compound have very small intensity
(f z 0) that is nearly forbidden by orbital symmetry considerations
(Table 4).
The calculated (UV/Vis) of the compound PA-101 in solvent DMF
and experimental spectrum at concentration 4.33$104 M/l and in
solvent DMF is shown in Fig. 5a and b. The calculated and experi-
mental values of maximum wavelength are 468 nm (f ¼ 1.76,
Fig. 5a) and 435 nm (Fig. 5b), respectively. As can be seen, the
calculated value of wavelength is in good agreement with the
experimental value.
2.3. Frontier molecular orbital analysis of the structures PA-100,
PA-101
The frontier molecular orbitals (FMO) analysis [15,21] plays an
important role in the electronic and optical properties, as well as in
UV/Vis spectrum and chemical reactions. FMO analysis was done
for the compounds PA-100 and PA-101 by B3LYP/6-31þG* level of
energy. HOMO and LUMO orbitals act as electron donor and
electron acceptor, respectively. The high amount of EHOMO indicates
the tendency of the compound to donate electron to acceptor
compound with low energy and the low amount of ELUMO shows
that the compound has more tendency to accept electrons. The
FMO results of the title compounds are summarized in Table 5.
As can be seen from Table 5, the energy values of HOMO of the
compounds PA-100 and PA-101 is 5.93 eV and 5.83 eV respec-
tively and their energy values of LUMO is 2.69 eV and 2.82 eV,
respectively. Total electronic densities of states (DOSs) [23] of the
title compounds were computed (Fig. 6). The DOS analysis indicates
that the HOMO-LUMO energy gaps (Eg) of the compounds PA-100
and PA-101 are about 3.24 eV and 3.01 eV, respectively. The com-
pound PA-100 has the higher energy gap value (3.24 eV) rather
than the compound PA-101 (3.01 eV), therefore PA-100 is less
reactive with the harder electronic transfers comparing with the
compound PA-101.
A detail of quantum molecular descriptors of the title com-
pounds such as ionization potential (I ¼ - EHOMO), electron affinity
(A ¼ - ELUMO), global hardness (h ¼ I _ A/2), electronegativity
(c ¼ I þ A/2), electronic chemical potential (m ¼ -(I þ A)/2), elec-
trophilicity (u ¼ m2/2h) [25] and chemical softness (S ¼ 1/h) [15] are
calculated and are listed in Table 5. The energy of HOMO is directly
related to the ionization potential (I), while the energy of LUMO is
related to the electron affinity (A). The global hardness (h) corre-
sponds to the HOMO-LUMO energy gap. A molecule with a small
energy gap has high chemical reactivity, low kinetic stability and is
a soft molecule, while a hard molecule has a large energy gap [15].
The global hardness (h) of the compounds PA-100, PA-101 is 1.62 eV
and 1.50 eV respectively. From these values can be understood that
the compound PA-100 has the higher global hardness, therefore it
is a hard molecule comparing with the PA-101. Electronegativity (c)
is a measure of the power of an atom or a group of atoms to attract
electrons [16] and the chemical softness (S) describes the capacity
of an atom or a group of atoms to receive electrons [15].
 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550
(a)
(b)
Fig. 3. UV/Vis spectrum of the compound PA-100 in solvent DMF: a) calculated by
TDB3LYP/6-31þG* method and b) experimental at concentration of dye 3.54$104 M/l.
The dipole moment parameter is used for investigation of
intermolecular interactions and study of asymmetric nature of
compounds also. The high amounts of dipole moment lead to
stronger intermolecular interaction [25]. As can be seen from
Table 5, PA-100 has the higher (7.5936 Debye) rather than PA-101
(5.7644 Debye). The magnitude of the dipole moment is related
to the composition and dimensionality of the 3D compounds. The
point group of the title compounds is C1, which refers to their high
asymmetry. When the atoms in compound are irregularly arranged
leads to the increasing dipole moment.
2.4. Molecular electrostatic potential (MEP) of the compounds PA-
100, PA-101
Molecular electrostatic potential (MEP) maps show the elec-
tronic density in the molecules. The MEP maps are also used to
identify sites of negative and positive electrostatic potentials for
electrophilic attack and nucleophilic reactions [15]. The difference
of the electrostatic potential at the surfaces is represented by
541
different colors. The negative regions (red, orange and yellow color)
of MEP with the high electron density were related to electrophilic
reactivity, the positive regions (blue color) with the low electron
density ones to nucleophilic reactivity and green color is neutral
regions. The MEPs of the compounds PA-100 and PA-101 were
obtained by theoretical calculations using the B3LYP/6-31þG* level
of energy (Fig. 7).
As shown in Fig. 7, the negative region (red color) of the com-
pound PA-100 is mainly focused on N10 atom and phenyl rings.
Therefore, these regions are suitable for electrophilic attack. Ac-
cording to MEP maps of the compound PA-101, the negative region
(red color) is mainly focused on N10 atom and non-substituted
phenyl rings. The parts of the title compounds with pale red or
yellow color are sites with weak interaction. The regions with green
color of the two compounds indicate areas with zero potential
(neutral sites).
2.5. Natural charge analysis of the compounds PA-100, PA-101
The atomic charges play an important role on molecular polar-
izability, dipole moment, electronic structure and related proper-
ties of molecular systems. We calculated the charge distributions
for equilibrium geometry of the compounds PA-100 and PA-101 by
the NBO (natural charge) charges [25] using B3LYP/6-31þG* level of
energy. The calculated natural charges are listed in Table 6 (Atoms
labeling is according to Fig. 1).
The total charge of the investigated compounds is equal to zero.
Also Fig. 8 shows results of natural charges in graphical form. The
results of natural charge (NBO) analysis of the compounds PA-100
and PA-101 show that carbon atoms have both positive and nega-
tive charges values. According to results, the positive carbons are
observed for the carbons atoms attachment to the electron-
withdrawing nitrogen atoms (C9, C11, C14, C19). The other carbon
atoms have negative charge. The highest positive charges of the
compound PA-100 is observed for hydrogen atoms and the highest
negative charge is observed for N10 atom in imine group.
As can be seen from Fig. 8, the positive carbons are observed for
the carbons atoms attachment to the electron-withdrawing nitro-
gen and oxygen atoms (C3, C9, C11, C14, C19). The other carbon
atoms have negative charge. The highest positive charge is
observed for the C3 atom (0.330e) due to the electron-withdrawing
nature of the O25 atom, therefore it is more acidic. The highest
negative charge is observed for the O25 atom (0.539e). The C26
atom of methyl group has the more negative charge (0.333e)
rather than other carbon atoms due to hyperconjugation effect.
2.6. NBO analysis of the compound PA-101
Natural bond orbital (NBO) analysis is important method for
studying intra- and inter-molecular bonding and interaction be-
tween bonds in molecular systems [27]. Electron donor orbitals,
acceptor orbitals and the interacting stabilization energy (E(2))
resulting from the second-order micro disturbance theory for the
compound PA-101 are reported in Table 7.
The electron delocalization from filled NBOs (donor orbitals) to
the empty NBOs (acceptor orbitals) describes a conjugative electron
transfer process between them. For each donor (i) and acceptor (j),
the stabilization energy E(2) associated with the delocalization i/j
is estimated [28]:
Fði; jÞ2
Eð2Þ ¼ DEij ¼ qi (1)
εj  εi
where qi is the donor orbital occupancy, εj and εi are diagonal
542 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550

Table 4
Electronic absorption spectrum of the compound PA-101 calculated by TDB3LYP/6-31þG* method.

Excited Wavelength Excitation Configurations Composition (corresponding transition orbitals) Oscillator

State (nm) Energy (eV) Strength (f)

S1 480 2.57 0.67(H-2/L) þ 0.20(H-2/Lþ1) 0.00

S2 468 2.64 0.70(H/L) 1.76
S3 381 3.25 0.59(H-1/L)  0.34 (H/Lþ1) 0.25
S4 347 3.56 0.35(H-1/L) þ 0.10(H-1/Lþ1) þ 0.59(H/Lþ1) 0.10
S5 320 3.86 0.19(H-6/L)  0.13(H-5/L) þ 0.40(H-4/L) þ 0.45(H-3/L)  0.14(H-1/Lþ1) 0.08
S6 318 3.88  0.10(H-6/L)  0.45(H-4/L) þ 0.48(H-3/L) 0.04
S7 312 3.96 0.16(H-7/L) þ 0.24(H-6/L) þ 0.14(H-2/Lþ1) þ 0.55(H-1/Lþ1)  0.12(H/Lþ1) 0.25
S8 306 4.04 0.14(H-7/L) þ 0.35(H-6/L)  0.16(H-4/L)  0.13(H-2/L) þ 0.43(H-2/Lþ1)  0.31(H-1/Lþ1) 0.00
S9 304 4.07  0.18(H-7/L)  0.36(H-6/L) þ 0.19(H-4/L)  0.14(H-2/L) þ 0.48(H-2/Lþ1) 0.00
S10 299 4.14 0.12(H-6/L) þ 0.61(H-5/L)  0.19(H-5/Lþ1) þ 0.17(H/Lþ2) þ 0.12(H/Lþ3) 0.00
S11 281 4.40 0.11(H-8/L) þ 0.57(H-7/L)  0.26(H-6/L) þ 0.13(H-4/L)  0.11(H-1/Lþ1)  0.12(H/Lþ5) 0.01
S12 273 4.53  0.28(H-5/L)  0.24(H-5/Lþ1) þ 0.53(H/Lþ2) þ 0.19(H/Lþ3) 0.02
S13 266 4.65  0.11(H-7/L) þ 0.11(H-6/Lþ1) þ 0.42(H-4/Lþ1) þ 0.21(H- 0.04
3/Lþ1) þ 0.15(H/Lþ2)  0.38(H/Lþ3)  0.15(H/Lþ4)
S14 262 4.71  0.12(H-7/L) - 0.15(H-7/Lþ1) - 0.11(H-6/L)  0.14(H-5/Lþ1) þ 0.37(H-4/Lþ1) þ 0.15(H- 0.03
3/Lþ1)  0.25(H/Lþ2) þ 0.39(H/Lþ3) þ 0.10(H/Lþ4)
S15 257 4.80 0.10(H-7/L) þ 0.24(H-7/Lþ1) þ 0.33(H-6/Lþ1)  0.15(H-5/Lþ1) þ 0.17(H-4/Lþ1) - 0.26(H- 0.00
3/Lþ1  0.10(H/Lþ2)  0.33(H/Lþ4) þ 0.12(H/Lþ5)
S16 256 4.83 0.19(H-7/Lþ1) þ 0.38(H-6/Lþ1)  0.11(H-5/Lþ1)  0.11(H-3/L) þ 0.22(H-3/Lþ1) þ 0.10(H- 0.00
1/Lþ4) þ 0.42(H/Lþ4)
S17 251 4.93 0.10(H-8/L) þ 0.17(H-6/Lþ1) þ 0.37(H-5/Lþ1) þ 0.17(H-4/Lþ1)  0.33(H- 0.02
3/Lþ1) þ 0.20(H/Lþ2) þ 0.14(H/Lþ3) þ 0.21(H/Lþ4)  0.18(H/Lþ5)
S18 249 4.96 0.16(H-6/Lþ1) þ 0.32(H-5/Lþ1)  0.12(H-4/Lþ1) þ 0.39(H-3/Lþ1) þ 0.27(H/Lþ3)  0.28(H/Lþ4) 0.07
S19 247 5.01 0.58(H-8/L)  0.10(H-7/L) þ 0.19(H-6/Lþ1)  0.13(H-5/Lþ1)  0.19(H- 0.00
4/Lþ1)  0.10(H/Lþ4)  0.14(H/Lþ5)
S20 244 5.07  0.42(H-2/Lþ2) þ 0.54(H-2/Lþ3) 0.00
*
H-HOMO, L-LUMO.

Fig. 4. Form of the MO involved in formation of absorption spectrum of the compound PA-101 at lmax ¼ 468 nm calculated by B3LYP/6-31þG* method.

elements and F(i,j) is the off diagonal NBO Fock matrix element. The
resonance energy (E(2)) detected the quantity of participation of
electrons in the resonance between atoms of molecule. The larger
E(2) value, the more intensive is the interaction between electron
donors and acceptor, i.e. the more donation tendency from electron
donors to electron acceptors and the greater the extent of conju-
gation of the whole system [27]. Delocalization of electron density
between occupied Lewis-type (bond or lone pair) NBO orbitals and
formally unoccupied (antibond or Rydberg) non Lewis NBO orbitals
correspond to a stabilization donor-acceptor interaction. NBO
analysis has been performed for the compound PA-101 by B3LYP/6-
31þG* method in order to elucidate the intramolecular, rehybrid-
ization and delocalization of electron density within the title
compound. The strong, moderate and weak intramolecular hyper-
conjugative interactions of the title compound such as p/p*,
p*/p*, p*/s*, s/s*, n/s* and n/p* transitions are presented
in Table 7. According to NBO analysis, the intramolecular hyper-
conjugative interactions of the p/p* have the moderate resonance
energy (E(2)). The p(C7eC8)/p*(C9eN10) transition has the
highest resonance energy (23 kcal/mol) rather than other p/p*
transitions of the compound PA-101. The other important intra-
molecular hyperconjugative interactions of the p/p* in phenyl
ring that lead to a moderate delocalization are such as
C5eC6/C1eC2, C9eN10/C11eC12, C11eC12/C13eC14,
C15eC16/C11eC12, C19eC24/N17eN18 with the strong
resonance energies (E(2)) 20.34 kcal/mol, 20.57 kcal/mol,
20.27 kcal/mol, 20.53 kcal/mol and 20.78 kcal/mol respectively. The
intramolecular hyperconjugative interactions of the p*/p*,
p*/s* and s/s* have the most resonance energy (E(2)) compared
with p/p* transitions. The strongest intramolecular hyper-
conjugative interaction of the p*/p*, p*/s* and s/s* is
observed for p*(C3eC4)/p*(C1eC2), p*(C3eC4)/s*(C26eH24),
s(C9eH33)/s*(C26eH44) with the strong resonance energies
(E(2)) 247.15 kcal/mol, 1125.15 kcal/mol, 5571.50 kcal/mol respec-
tively, that lead to stability of the title compound. The highest
resonance energy of the title compound is observed for
s(N18eC19)/p*(C5eC6) transition with resonance energy (E(2))
33245.41 kcal/mol that lead to most stability of the title compound.
The strongest n/s* and n/p* transitions are due to n1(N10)/
s*(C5eC6), n1(N1)/s*(C6eC7) and n2(O25)/p*(C3eC4) in-
teractions with stabilization energies of 95.59 kcal/mol, 36.27 kcal/
mol and 31.29 kcal/mol respectively.
The results of NBO analysis such as the occupation numbers
with their energies for the interacting NBOs [interaction between
natural bond orbital A and natural bond orbital B (A-B)] and the
polarization coefficient amounts of atoms in the compound PA-101
are presented using the B3LYP/6-31þG* method is summarized in
Table 8 (Atoms labeling is according to Fig. 1).
The size of polarization coefficients shows the importance of the
two hybrids in the formation of the bond in molecular system. The
 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550 543

from Table 8, the calculated bonding orbital for the s(C3eO25)

bond is the s ¼ 0.5705(sp2.98)þ0.8213(sp1.96) with high occupancy
1.99297a.u. and low energy 0.92573a.u. The polarization co-
efficients of C23 ¼ 0.5705 and O24 ¼ 0.8213 shows importance of
O25 in forming s(C3eO25) bond compared with C3 atom. As seen
from Table 8, the calculated bonding orbital for the s(C9eN10)
bond is s ¼ 0.6365(sp2.03)þ0.7713(sp1.58) is formed from sp2.03 and
sp1.58 hybrids on C9 and N10 atoms which is the mixture of
s(32.93%) p(67.01%) and s(38.65%) p(61.15%). According to NBO
analysis, the natural hybrid orbital n1(N10) occupy a higher energy
orbital (0.39127 a.u) with high occupation number (1.88759 a.u)
and high p-character (71.67%). Therefore n1(N10) participates as
electron donation to s*(C5eC6) and s*(C6eC7) in the n1(N10)/
s*(C5eC6) and n1(N10)/s*(C6eC7) interactions with high reso-
nance energies (E(2)) 95.59 kcal/mol and 36.27 kcal/mol in the title
compound (see Table 7). The natural hybrid orbital n2(O25) with
high occupancy 1.82995 a.u. and high energy 0.32540 a.u. has p-
character (99.91%). Therefore pure p-type lone pair orbital n2(O25)
participates as electron donation to p*(C3eC4) and s*(C6eC7) in
the n2(O25)/p*(C3eC4) and n2(O25)/s*(C6eC7) interaction
(a)
with high resonance energy (E(2)) 31.29 kcal/mol and 12.16 kcal/mol
in the title compound (see Table 7).

2.7. Vibrational frequencies of the compounds PA-100, PA-101

In order to confirm the accuracy of our findings, IR spectroscopy

was used. The theoretical IR spectra of the optimized compounds
PA-100 and PA-101 was calculated using B3LYP/6-31þG* level of
energy. The important calculated and experimental vibrational
frequencies of the PA-100 and PA-101 are summarized in Tables 9
and 10 respectively. The experimental and calculated spectra of
the title compounds are found to be in good agreement with each
other.
The C]N bond stretching vibrations appear in the region 1700-
1500 cm1 which is used to identify Schiff bases [29]. The experi-
mental and calculated amounts of the C]N (HeC]N group)
stretching vibration of the compound PA-100 is assigned at
1626 cm1 and 1676 cm1, respectively. Also the C]C aromatic ring
stretching vibrations are expected in the range 1650e1200 cm1
[30]. In the FTeIR spectrum of the compound PA-100, the C]C
(b) stretching vibrations are assigned in the range 1626e1412 cm1
and the corresponding theoretical values are observed in the region
Fig. 5. UV/Vis spectrum of the compound PA-101 in solvent DMF: a) calculated by
1676-1451 cm1. The CeH stretching vibrations of aromatic com-
TDB3LYP/6-31þG* method and b) experimental at concentration of dye 4.33$104 M/l.
pounds are expected in the range 3100e3000 cm1 and are not
affected by the nature of substituents on the aromatic rings [31].
Table 5 The CeH aromatic bending vibrations out of plane are appeared in
Electronic properties of the compounds PA-100 and PA-101 calculated by B3LYP/6- the region 1000-700 cm1 [32]. The aromatic CeH in-plane
31þG* method bending vibrations are expected in the region 1500e1100 cm1
Property PA-100 PA-101 [33]. The asymmetric CeH stretching vibrations of the aromatic
ring of the PA-100 are assigned at 3060 cm1, 3025 cm1 and cor-
EHOMO (eV) 5.93 5.83
ELUMO (eV) 2.69 2.82 responding theoretical values are 3209 cm1, 3199 cm1 respec-
Energy gap (eV) 3.24 3.01 tively. The frequencies observed for vibrations out of plane in the
Ionization potential, I (eV) 5.93 5.83 FTeIR spectrum in the region 1018-570 cm1 are in good agree-
Electron affinity, A (eV) 2.69 2.82
ment with the calculated values such as 1030-607 cm1. Also the
Electronegativity, c (eV) 4.31 4.32
Global hardness, h (eV) 1.62 1.50 calculated values of vibrations in-plane in the region 1359-
Chemical potential, m (eV) 4.31 4.32 1070 cm1 are good agreement with the experimental frequencies
Global electrophilicity, u (eV) 5.73 6.22 of aromatic ring such as 1414-1105 cm1, respectively (see Table 9).
Chemical softness, S (eV1) 0.61 0.66 The azo group (N]N) stretching vibration in azo compounds shows
Dipole moment (Debye) 7.5936 5.7644
important bands in the region 1400-1600 cm1 [34]. The N]N
Point group C1 C1
stretching vibration of PA-100 is assigned at 1577 cm1, 1569 cm1,
1488 cm1 and the corresponding theoretical value is 1626 cm1,
1622 cm1, 1575 cm1 respectively. These data indicates the pres-
differences in electronegativity of the atoms involved in the bond
ence of the compound PA-100 (Table 9).
formation are reflected in the larger differences in the polarization
In FT-IR spectrum of the compound PA-101, the N]N stretching
coefficients of the atoms (CeO, CeN, CeH bonds). As can be seen
vibrations is assigned at 1597-1413 cm1 and the corresponding
544 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550

Fig. 6. Calculated DOS plots of the compounds PA-100 and PA-101.

Fig. 7. Molecular electrostatic potential (MEP) map of the compounds PA-100 and PA-101 calculated by B3LYP/6-31þG*.

Table 6
Natural Charges distribution (NBO charges, e) of the compounds PA-100 and PA-101.

PA-100 PA-101

Atoms Charge Atoms Charge Atoms Charge Atoms Charge

C1 0.207 C24 0.245 C1 0.190 C24 0.216

C2 0.245 H25 0.251 C2 0.282 O25 0.539
C3 0.230 H26 0.255 C3 0.330 C26 0.333
C4 0.243 H27 0.254 C4 0.305 H27 0.253
C5 0.207 H28 0.255 C5 0.187 H28 0.260
C6 0.104 H29 0.248 C6 0.135 H29 0.257
C7 0.156 H30 0.244 C7 0.148 H30 0.251
C8 0.276 H31 0.245 C8 0.291 H31 0.243
C9 0.093 H32 0.201 C9 0.095 H32 0.244
N10 0.477 H33 0.258 N10 0.489 H33 0.201
C11 0.127 H34 0.260 C11 0.141 H34 0.253
C12 0.233 H35 0.261 C12 0.259 H35 0.262
C13 0.222 H36 0.255 C13 0.218 H36 0.258
C14 0.047 H37 0.258 C14 0.064 H37 0.257
C15 0.230 H38 0.256 C15 0.205 H38 0.261
C16 0.254 H39 0.255 C16 0.246 H39 0.254
Fig. 8. Natural charges distribution of the title compounds.
N17 0.154 H40 0.256 N17 0.205 H40 0.254
N18 0.159 H41 0.259 N18 0.216 H41 0.255
C19 0.055 C19 0.076 H42 0.256 symmetric CeH stretching vibrations of the methyl group (CH3).
C20 0.236 C20 0.231 H43 0.244 The experimental values of the asymmetric and symmetric
C21 0.238 C21 0.242 H44 0.220
C22 0.240 C22 0.227 H45 0.220
stretching vibrations are assigned at 2923 cm1 and 2661 cm1
C23 0.238 C23 0.248 respectively, whereas corresponding theoretical values is
3116 cm1 and 3047 cm1 respectively. These data indicates the
presence of the compound PA-101 (Table 10).

theoretical value is 1612e1452 cm1. The experimental and calcu-

lated values of the CeO stretching vibration are assigned at
1230 cm1 and 1289 cm1, respectively. The symmetric CeH
stretching vibrations of the aromatic ring are assigned at of
3205 cm1 and corresponding theoretical value is appeared at
3234 cm1 and the asymmetric CeH stretching vibrations of the
aromatic ring are assigned at 3061 cm1 and corresponding theo-
retical value is appeared at 3199 cm1. The other important vibra-
tion mode of the compound PA-101 is the asymmetric and
3. Experimental details
3.1. Reagent and apparatus
All chemicals used were of analytical reagent grade. PVA used in
this work «Mowiol 28e99» was purchased from Hoe €chst Akien-
gesllschaft Co. (Germany). The experimental UV absorption spectra
of the title molecules were recorded on UVeVisible Spectropho-
tometer Cary 300 (Varian, USA). The optical transmission spectra
 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550 545

CHO 2

1 N
R1
N NH2 +
MeOH, AcOH

R2

N N
R2 = H, OCH3
N

Fig. 9. Scheme of synthesis of the compounds PA-100 and PA-101.

Table 7
Significant donor-acceptor interactions and second order perturbation energies of the compound PA-101 calculated using the B3LYP/6-31þG* level of energy.

Donor (i) Occupancy Acceptor (j) Occupancy E(2)a kcal/mol E(j)-E(i)b a.u. F(i, j)c a.u.

p(C5eC6) 1.61590 p*(C1eC2) 0.29806 20.34 0.27 0.068

p*(C3eC4) 0.39991 18.71 0.26 0.063
p*(C7eC8) 0.15616 17.36 0.23 0.060
p(C7eC8) 1.80626 p*(C7eC8) 0.15616 0.67 0.25 0.012
p*(C9eN10) 0.20586 23.00 0.29 0.073
p(C9eN10) 1.98796 p*(C7eC8) 0.15616 19.11 0.31 0.062
p*(C11eC12) 0.40295 20.57 0.35 0.063
p(C11eC12) 1.58134 p*(C13eC14) 0.41145 20.27 0.34 0.074
p(C13eC14) 1.59010 p*(C11eC12) 0.40295 19.51 0.27 0.065
p*(C15eC16) 0.29560 19.52 0.28 0.068
p*(N17eN18) 0.23860 16.86 0.22 0.057
p(C15eC16) 1.67841 p*(C11eC12) 0.40295 20.53 0.28 0.069
p*(C13eC14) 0.41145 17.45 0.28 0.064
p(C19eC24) 1.61588 p*(N17eN18) 0.23860 20.78 0.23 0.064
p*(C3eC4) 0.39991 p*(C1eC2) 0.29806 247.15 0.01 0.080
p*(C5eC6) 0.40109 s*(C4eC5) 0.01270 772.11 0.44 1.150
s*(C5eC6) 0.02466 203.05 0.98 0.863
s*(C26eH24) 0.01655 1125.15 0.28 1.095
s(C1eC6) 1.97563 s*(C4eC5) 0.01270 148.58 0.05 0.074
s(C1eH27) 1.98080 s*(C4eC5) 0.01270 5250.96 0.05 0.445
s*(C5eC6) 0.02466 163.17 0.58 0.276
s(C2eC3) 1.97546 s*(C4eC5) 0.01270 141.94 0.06 0.085
s(C3eC4) 1.97937 s*(C4eC5) 0.01270 187.46 0.08 0.110
s(C3eO25) 1.99292 s*(C26eH44) 0.01655 183.74 0.11 0.127
s(C9eH33) 1.98351 s*(C4eC5) 0.01270 2084.05 0.28 0.683
s*(C5eC6) 0.02466 384.60 0.82 0.501
s*(C26eH44) 0.01655 5571.50 0.12 0.715
s(C11eC16) 1.97482 s*(C4eC5) 0.01270 1452.79 1.20 1.182
s*(C26eH44) 0.01655 1846.42 1.03 1.237
s(N18eC19) 1.98110 s*(C26eH44) 0.01655 1892.44 0.29 0.662
s(C19eC20) 1.97897 s*(C4eC5) 0.01270 1483.79 2.48 1.716
s*(C26eH44) 0.01655 1750.99 2.32 1.799
s(N18eC19) 1.98110 p*(C5eC6) 0.40109 33245.41 0.01 0.598
n1(N10) 1.88759 s*(C5eC6) 0.02466 95.59 0.28 0.148
s*(C6eC7) 0.02082 36.27 0.43 0.114
n1(N17) 1.94947 s*(C13eC14) 0.03392 8.88 0.96 0.083
n1(N18) 1.95105 s*(C19eC20) 0.03354 8.72 0.96 0.082
n1(O25) 1.96415 s*(C3eC4) 0.03019 10.63 0.99 0.092
n2(O25) 1.82995 p*(C3eC4) 0.39991 31.29 0.33 0.097
s*(C6eC7) 0.02082 12.16 0.36 0.062
a
E(2) Energy of hyperconjucative interactions.
b
Energy difference between donor and acceptor i and j NBO orbitals.
c
F(i, j) Is the Fock matrix element between i and j NBO orbitals.
546 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550

Table 8
Calculated natural bond orbitals (NBO) and the polarization coefficient for each hybrid in selected bonds of the compound PA-101 using the B3LYP/6-31þG* level of energy.

Occupancy (a.u.) Bond (A-B)a Energy (a.u.) EDA (%) EDB (%) NBO S(%) (A) S(%) (B) P(%) (A) P(%) (B)

1.97760 s(C1eC2) 0.71153 49.86 50.14 0.7061 (sp1.81) þ 0.7081 (sp1.78) 35.53 35.93 64.43 64.03
1.99297 s(C3eO25) 0.92573 32.55 67.45 0.5705 (sp2.98) þ 0.8213 (sp1.96) 25.06 33.75 74.75 66.18
1.99281 s(O25eC26) 0.84783 69.17 30.83 0.8317 (sp2.48) þ 0.5552 (sp4.01) 28.68 19.91 71.26 79.83
1.97479 s(C5eC6) 0.69773 48.83 51.17 0.6988 (sp1.89) þ 0.7153 (sp1.97) 34.53 33.71 65.43 66.26
1.61590 p(C5eC6) 0.25467 46.19 53.81 0.6796 (sp1.00) þ 0.7335 (sp1.00) 0.00 0.00 99.96 99.99
1.80626 p(C7eC8) 0.27584 46.79 53.21 0.6841 (sp1.00) þ 0.7294 (sp1.00) 0.00 0.00 99.94 99.95
1.98796 s(C9eN10) 0.87697 40.52 59.48 0.6365 (sp2.03) þ 0.7713 (sp1.58) 32.93 38.65 67.01 61.15
1.88321 p(C9eN10) 0.33310 38.71 61.29 0.6222 (sp99.99) þ 0.7829 (sp99.99) 0.27 0.28 99.62 99.51
1.98280 s(N10eC11) 0.78471 58.51 41.49 0.7649 (sp2.04) þ 0.6441 (sp2.41) 32.89 29.29 66.95 70.66
1.97586 p(C11eC12) 0.70179 48.02 51.98 0.6930 (sp1.00) þ 0.7210 (sp99.99) 0.00 0.01 99.96 99.95
1.59010 p(C13eC14) 0.25825 46.87 53.13 0.6847 (sp1.00) þ 0.7289 (sp1.00) 0.00 0.00 99.95 99.99
1.98139 s(C14eN17) 0.78489 41.36 58.64 0.6431 (sp2.50) þ 0.7658 (sp2.08) 28.52 32.40 71.37 67.52
1.98698 s(N17eN18) 0.96668 50.07 49.93 0.7076 (sp2.25) þ 0.7066 (sp2.25) 30.77 30.75 69.11 69.13
1.91088 p(N17eN18) 0.37638 49.62 50.38 0.7044 (sp1.00) þ 0.7098 (sp1.00) 0.00 0.00 99.74 99.74
1.98110 s(N18eC19) 1.10723 58.59 41.41 0.7655 (sp2.13) þ 0.6435 (sp2.54) 31.93 28.19 67.98 71.71
1.61588 p(C19eC24) 0.26157 51.96 48.04 0.7208 (sp1.00) þ 0.6931 (sp1.00) 0.00 0.00 99.98 99.96
1.97850 s(C15eC16) 0.70926 50.03 49.97 0.7073 (sp1.81) þ 0.7069 (sp1.82) 35.52 35.47 64.44 64.49
1.67841 p(C15eC16) 0.26160 48.43 51.57 0.6959 (sp1.00) þ 0.7181 (sp1.00) 0.00 0.00 99.95 99.95
1.98080 s(C1eH27) 0.69898 62.73 37.27 0.7920 (sp2.34) þ 0.6105 (s) 29.91 100 70.03 e
1.97574 s(C7eH31) 0.53119 62.26 37.74 0.7891 (sp2.55) þ 0.6143 (s) 28.15 100 71.79 e
1.97915 s(C13eH35) 0.52928 63.35 36.65 0.7960 (sp2.25) þ 0.6054 (s) 30.76 100 69.20 e
1.98261 s(C21eH39) 1.03614 62.85 37.15 0.7928 (sp2.31) þ 0.6095 (s) 30.20 100 69.75 e
1.99109 s(C26eH43) 0.52357 62.24 37.76 0.7889 (sp2.77) þ 0.6145 (s) 26.52 100 73.41 e
1.88759 n1(N10) 0.39127 e e sp2.54 28.20 e 71.67 e
1.94947 n1(N17) 0.41392 e e sp1.67 37.36 e 62.58 e
1.95105 n1(N18) 0.41669 e e sp1.64 37.91 e 62.03 e
1.96415 n1(O25) 0.57513 e e sp1.66 37.59 e 62.35 e
1.82995 n2(O25) 0.32540 e e sp1.00 0.00 e 99.91 e
a
A-B is the bond between atom A and atom B. (A: natural bond orbital and the polarization coefficient of atom; A-B: natural bond orbital and the polarization coefficient of
atom B).

Table 9 Table 10
Experimental and calculated vibrational frequencies and their assignment of the Experimental and calculated vibrational frequencies and their assignment of the
compound PA-100 by using B3LYP/6-31þG* method. compound PA-101 by using B3LYP/6-31þG* method.

nexp. (cm1) ncal. (cm1) IR intensity Assignment nexp. (cm1) ncal. (cm1) IR intensity Assignment

570 607 13.70 uC-H(arom) 491 533 34.33 uC-H(arom)

687 706 96.54 uC-H(arom) 545 567 29.36 uC-H(arom)
731 767 60.72 uC-H(arom) 688 720 1.11 tC-H(arom)
751 772 76.02 uC-H(arom) 768 781 54.17 uC-H(arom)
767 831 29.72 tC-H(arom) 832 869 73.19 uC-H(arom)
843 854 27.45 uC-H(arom) 1067 1102 11.28 bC-H(arom)
851 893 10.86 tC-H(arom) 1118 1157 651.21 bC-H(arom)
917 933 32.77 tC-H(arom) 1138 1177 358.17 bC-H(arom), nC-N
956 989 7.76 tC-H(arom) 1230 1289 933.98 nC-O, bC-H(arom), bC-H (N]CeH)
986 1011 2.62 tC-H(arom) 1305 1325 26.36 bC-H(arom), bC-H (N]CeH)
1018 1030 78.21 uC-H 1413 1452 61.09 nC ¼ C, nN ¼ N
1070 1105 19.03 bC-H(arom) 1445 1483 44.49 nC ¼ C, nN ¼ N
1102 1139 15.82 bC-H(arom) 1461 1506 34.07 nC ¼ C, nN ¼ N
1138 1174 138.09 nC-N, bC-H(arom) 1504 1539 472.84 nC ¼ C, nC ¼ N, nN ¼ N
1152 1185 7.60 bC-H(arom) 1575 1600 173.18 nC ¼ C, nC ¼ N, nN ¼ N
1222 1253 1.64 nC-N, bC-H 1597 1612 2516.29 nC ¼ C, nC ¼ N, nN ¼ N
1257 1294 58.29 bC-H (N]CeH), bC-H 1617 1676 180.03 nC ¼ C, nC ¼ N
1305 1333 11.71 bC-H(arom) 2661 3047 110.25 nC-H sym(CH3)
1359 1414 36.93 bC-H (N]CeH), bC-H 2734 3055 44.22 nC-H (N]CeH)
1412 1451 4.86 nC ¼ C 2923 3116 45.50 nC-H asym(CH3)
1439 1489 16.65 nC ¼ C 3061 3199 23.96 nC-H asym(arom)
1447 1526 60.19 nC ¼ C 3205 3234 21.02 nC-H sym(arom)
1488 1575 599.45 nC ¼ C, nC ¼ N, nN ¼ N
Abbreviations: n, stretching; b, in plane bending; u, out of plane bending; t, torsion;
1569 1622 241.04 nC ¼ C, nC ¼ N, nN ¼ N
sym, symmetric deformation; asym, asymmetric deformation; arom, aromatic.
1577 1626 221.91 nC ¼ C, nC ¼ N, nN ¼ N
1602 1661 129.64 nC ¼ C, nC ¼ N
1626 1676 346.93 nC ¼ C, nC ¼ N
2910 3057 53.10 nC-H (N]CeH)
were measured in polarized light with UV-NIR Spectrophotometer
3025 3199 1328 nC-H asym(arom)
3060 3209 50.42 nC-H asym(arom) HR4000 (Ocean optics, USA). Experimental IR-spectra of films was
recorded in the frequency region 400-4000 cm1 on a Spectro-
Abbreviations: n, stretching; b, in plane bending; u, out of plane bending; t, torsion;
asym, asymmetric deformation; arom, aromatic. photometer of Protege
 460 (Nicolet, US). Thermal and electrical
conductivity of films was measured on the complex equipment LC
e 201 (Alfa Laval Group, Sweden) using indicator method of
 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550
determining the thermal and electrical conductivity of polymer
materials and thin films.
3.2. Preparation of polarizing PVA-films
The PVA-films were prepared from (wt. %) 10 PVA solution
containing 0.01e0.03 PA-100 and PA-101 (0.10e0.30 in film), 0.01
boric acid (H3BO3), 6.0 ethyl alcohol (C2H5OH) and water. An initial
composition was prepared by dissolving PVA in distilled water and
ethyl alcohol. The composition was mixed at temperature
85e90  C. The compounds PA-100 and PA-101 and additives were
added after 3 h after starting of heating PVA solution at intervals
20 min. The mixture was heated for 3 h. The hot solution was
filtered through two layers of technical nylon. Deaeration was
occurred during 12e15 h. The composition was cast on the pol-
ished glasses and dried in the closed box at temperature 20e22  C.
Uniaxial orientation was done in the 4% boric acid solution at
temperature 42e45  C. The washed film was dried for 30 min at
temperature 60e63  C. The value of Stretching Degree (Rs) was
determined as the ratio between length of the films after and
before (laft/lbef) uniaxial orientation. The thickness of the resulting
films was between 50 and 55 mm [1,2]. The film thickness was
measured with a micrometer with an accuracy of ± 5 mm (GS SSSR
6507-90).
Accuracy of measurements in this research limits the accuracy of
the results:
- Sample of the starting composition for preparation of solutions
and films for casting taken on an analytical balance accurate to
0.0005 g;
- Temperature measurement error was:
± 2.0  C in the preparation of polymer solutions with
additives,
± 1.0  C in the chemical treatment of the films,
± 3.0  C at thermal fixation and drying films;
- Relative error of spectrophotometric analysis did not exceed
1.0% and thermal conductivity 0.1%.
The standard deviation of parallel measurements determined by
formula [21e23]:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
. ffi
X not change (Figs. 5b and 11). Dichroism (anisotropy of absorption)
SðdÞ ¼ ðdi  dÞ2 n  1
i
where di - the result of a single measurement,
d - Arithmetic mean
n - Number of measurements.
3.3. synthesis of the compounds PA-100, PA-101
PA-100: A mixture of 4-aminoazobenzne (1) (2.6 mmol) and
aldehyde (2) (2.1 mmol) in 35 ml methanol was prepared. Then 2
drops of glacial acetic acid was added to the mixture and was
refluxed for 1 h. The hot solution was filtered through a paper filter,
cooled and left for 15 h at 4e6  C. The solid was dissolved in cold
methanol and washed with water and dried at 22e25  C.
PA-101: A mixture of 4-aminoazobenzne (1) (2.3 mmol) and
aldehyde (2.2) (2 mmol) in 35 ml methanol was prepared. Then 3
drops of glacial acetic acid was added to the mixture and was
refluxed for 2 h. The hot solution was filtered through a paper filter,
cooled and left for 12 h at 2e4  C. The solid was dissolved in cold
methanol and washed with water and dried at 22e25  C.
547
3.4. Polarization properties of PVA-films containing the compounds
PA-100, PA-101
The main optical properties of polarizing films such as Trans-
mittance (Tmax, Tmin), Polarizing Efficiency (PE) and Dichroic Ratio
(Rd) were evaluated at the absorption maximum of the polarizing
films according to Eqs. (3,4) [17]:
PE ¼ (Tmax e Tmin) / (Tmax þ Tmin) * 100 (3)
Rd ¼ Dmax / Dmin (4)
Where, Tmax, Tmin, Dmax and Dmin - Absorbance and Transmittance
for linearly polarized light parallel and perpendicular to direction of
stretching of colored PVA-film. Multi-angle spectral photometric
measurements were performed for all samples in the spectral range
from 200 to 600 nm at incidence angles of 7, 10 , 20 , 30 , and 40
for s- and p-polarized light. In all optical characterization and
reverse-engineering procedures throughout this study, we used
measurement data taken in the spectral range from 300 to 500 nm
only. Polarizing Efficiency (PE) of colored oriented PVA-films de-
pends on the concentration of injected PA-100 and PA-101 and
Stretching Degree (Rs ¼ 3.5) of the films, therefore the optimum
concentration of the PA-100 and PA-101 in PVA-film was obtained
(Figs. 10 and 11, Table 11).
PA-100: Changes in concentration of the PA-100 from 0.10 to
0.30 wt % in the colored oriented PVA-film show that with
increasing concentration of the PA-100, maximum light trans-
mission in parallel and perpendicular direction are reduced. At [PA-
100] ¼ 0.30 wt % Tmax ¼ 79.0%, Tmin ¼ 16.7%. PVA-film effectively
polarizes the light at 390e405 nm of spectrum with PE ¼ 70.6%.
Rd ¼ Dmax/Dmin ¼ 0.8/0.1 ¼ 8.0 (Table 11, Fig. 12). Absorption peak of
the PA-100 in PVA matrix does not change (Figs. 3b and 10).
PA-101: Changes in concentration of the PA-101 from 0.10 to
0.30 wt % in the colored oriented PVA-film show that with
increasing concentration of the PA-101, maximum light trans-
mission in parallel and perpendicular direction are reduced. At [PA-
101] ¼ 0.30 wt % Tmax ¼ 58.3%, Tmin ¼ 0.1%. PVA-film effectively
polarizes the light from UV (380 nm) to Visible region (450 nm) of
spectrum with PE ¼ 99.7%. Rd ¼ Dmax/Dmin ¼ 3.0/0.2 ¼ 15.0
(Table 11, Fig. 13). Absorption peak of the PA-101 in PVA matrix does
(2) (Figs. 12 and 13) appears under uniaxial orientation of the colored
Fig. 10. Transmission spectra and polarizing efficiency of the film containing 0.3 wt %
of PA-100.
548 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550

Table 12
Dependence of thermal conductivity on stretching degree in pure PVA-films.

Rs l, W/m. C
l|| l⊥ l||/l⊥
1.5 0.88 0.76 1.16
2 0.88 0.64 1.38
2.5 0.88 0.55 1.60
3 0.88 0.50 1.75
4 0.88 0.48 1.86

reported that special paints were used to sharply change the initial
color at a critical temperature (Tcr). The isothermal surface moves at
a certain speed in the proportion to a local gradient of the tem-
perature field. Thermo-physical characteristics of material can be
judged by the speed of isotherm movement and the form of flowed
surface. Thermal indicators of Ciba Com. (Switzerland) with small
sizes of Tcr in order to avoid thermal destruction of polymer ma-
Fig. 11. Transmission spectra and polarizing efficiency of the film containing0.3 wt % of terial were used. Thermal indicator is put on a film by a thin layer
PA-101.
and at regular intervals by a draw plate. Then, after some drying
period its unpainted surface is resulted on some time (30 s) in
Table 11
dense contact to a dot source of heat (it is heated up approximately
Main optical parameters of PVA-films containing PA-100 and PA-101 at lmax to 55  C metal needles). Thermo-physical properties of films was
determined by thermal conductivity of samples in parallel (l||) and
Films Dmax Dmin Tmax Tmin PE Rd
perpendicular (l⊥) directions of stretching axis. In case of aniso-
% tropic materials the ellipse a ratio of which axes is proportional to
PVA þ PAZB-100 0.8 0.1 79.0 16.7 70.6 8.0 thermal conductivity of a film lengthways and perpendicularly to
PVA þ PAZB-101 3.0 0.2 58.3 0.1 99.7 15.0 axis of its stretching is drawn. During this work, it was established
that the oriented PVA-films with new synthesized azomethines
have the phenomenon of anisotropy of thermal conductivity (l||/l⊥).
PVA-films. Thermal conductivity in a direction of orientation (l||) is higher
than in a direction perpendicular orientations (l⊥). On resulting
3.5. Anisotropy of thermal conductivity of the PVA-films containing anisotropy at a known degree of extension it is possible to judge
the compounds PA-100 and PA-101 anisotropy of chain structure. It has been noticed that during
thermal expansion and thermal conductivity geometric parameters
In the present study, we have studied thermal conductivity of of molecule, intermolecular forces play a significant role. In
the PVA systems containing new synthesized azomethines PA-100 unstretched PVA-film anisotropy of thermal conductivity is not
and PA-101. It is very important parameter for creation of ther- observed appreciably (l|| ¼ 0.87 W/m. C; l⊥ ¼ 0.87 W/m. C; l||/
mostable polarizing films. In the earlier researches [17,18] we l⊥ ¼ 1.00) whereas in stretched PVA-film anisotropy of thermal

Field of
Dichroism

(a) (b)
Fig. 12. Stretched colored PVA-films containing the 0.30 wt % of PA-100 in parallel (a) and perpendicular (b) directions of stretching.

Field of
Dichroism

(a) (b)
Fig. 13. Stretched colored PVA-films containing the 0.30 wt % of PA-101 in parallel (a) and perpendicular (b) directions of stretching.
 S. Shahab et al. / Journal of Molecular Structure 1157 (2018) 536e550 549

Table 13 Table 16
Thermal conductivity of PVA-films containing the PA-100 at concentration 0.3 wt%. Electrical conductivity of PVA-films containing PA-100 and PA-101 at concentration
0.3 wt%.
Rs l, W/m. C
PVA-films Rs d, S.cm1
l|| l⊥ l||/l⊥
d||, S.cm1 d⊥, S.cm1 d||/d⊥
2.0 0.86 0.26 3.31
3.0 0.85 0.24 3.54 PA-100 2.0 3.1∙10 5
5.1∙10 4
6.1∙10
4.0 0.84 0.18 4.67 3.0 5.9∙107 4.5∙102 1.3∙105
5.0 0.83 0.09 9.22 4.0 7.3∙107 4.9∙101 1.5∙106
5.0 4.0∙108 2.7∙101 1.5∙107
PA-101 2.0 6.9∙105 3.2∙104 2.2∙101
3.0 8.1∙107 4.6∙102 1.8∙105
Table 14 4.0 7.6∙108 6.0∙101 1.3∙107
Thermal conductivity of PVA-films containing the PA-101 at concentration 0.3 wt%. 5.0 2.8∙109 4.2∙10 0.7∙109

Rs l, W/m. C
l|| l⊥ l||/l⊥
orientation, it has increased, and in perpendicular axis it is reduced.
2.0 0.86 0.21 4.10
Anisotropy of electrical conductivity of PVA-films was defined as
3.0 0.85 0.13 6.54
4.0 0.84 0.09 9.33 (d||/d⊥) and is presented in Table 16.
5.0 0.83 0.07 11.86 The obtained data suggest that in the PVA films containing PA-
101, anisotropy of electrical conductivity is stronger than in the PVA
films containing PA-100.
conductivity is observed (Table 12).
When we inject the PA-100 and PA-101 in PVA-film there is 4. Conclusion
change in its thermal conductivity (Tables 13 and 14). It has been
found that along an axis of orientation, it has increased, and in Density functional theory (DFT/B3LYP/6-31þG*) were modeled
perpendicular axis it is reduced. Results of thermal conductivity 2 new azomethine dyes (PA-100, PA-101) absorbing in the visible
measurements of the PVA-films containing the PA-100 and PA-101 region of spectrum. These azomethine dyes were synthesized after
depending on stretching degree are presented in Tables 13 and 14 spending quantum chemical studies. On the basis of PVA and the
The occurrence of anisotropy of thermal conductivity is con- synthesized azomethine dyes were developed polarizing films
nected that at orientation of the PVA-film occurs orientation of the operating at visible region of spectrum. Polarizing efficiency of
amorphous part of polymer and also formation of additional colored oriented PVA-films depends on the concentration of
number of intermolecular connections. Thermal conductivity of the injected dye and stretching degree of the films was found. Polar-
PVA-films changes after the injection of dyes (Tables 13 and 14) and izing PVA-films containing the azomethine dye PA-101 have
along an axis of orientation and in perpendicular axis decreases. PE  97% at concentration 0.3 wt % and Rs ¼ 3.5. Stretched colored
PVA-films by new dichroic structures have phenomenon of
anisotropy of thermal and electrical conductivity. Thermal and
3.6. Anisotropy of electrical conductivity of PVA-films containing electrical conductivity in a direction of orientation is higher than in
PA-100 and PA-101 direction perpendicular orientations.

In the present section, we have studied electrical conductivity of

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