Synthesis, spectroscopic investigation and theoretical studies of 2-((E)-(2-(2-cyanoacetyl)hydrazono)methyl)-4-((E)-phenyldiazenyl)phenyl methyl carbonate

Article abstract of DOI:10.1016/j.molstruc.2016.12.051

Synthesis and computational optimization studies have been carried out by Hartree–Fock (HF) and Density Functional Theory (DFT–B3LYP) methods with 6–31+G(d, p) basis set for 2-((E)-(2-(2-cyanoacetyl)hydrazono)methyl)-4-((E)-phenyldiazenyl)phenyl methyl ca

Full text of DOI:10.1016/j.molstruc.2016.12.051

Accepted Manuscript
Synthesis, spectroscopic investigation and theoretical studies of 2-((E)-(2-(2-
cyanoacetyl)hydrazono)methyl)-4-((E)-phenyldiazenyl)phenyl methyl carbonate
A. Arokiasamy, G. Manikandan, V. Thanikachalam, K. Gokula Krishnan
PII:
S0022-2860(16)31368-0
10.1016/j.molstruc.2016.12.051
MOLSTR 23249
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 13 July 2016
Revised Date: 19 December 2016
Accepted Date: 20 December 2016
Please cite this article as: A. Arokiasamy, G. Manikandan, V. Thanikachalam, K. Gokula
Krishnan, Synthesis, spectroscopic investigation and theoretical studies of 2-((E)-(2-(2-
cyanoacetyl)hydrazono)methyl)-4-((E)-phenyldiazenyl)phenyl methyl carbonate, Journal of Molecular
Structure (2017), doi: 10.1016/j.molstruc.2016.12.051.
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ACCEPTED MANUSCRIPT
Synthesis, spectroscopic investigation and theoretical studies of
2-((E)-(2-(2-cyanoacetyl)hydrazono)methyl)-4-((E)-
phenyldiazenyl)phenyl methyl carbonate
A. Arokiasamya, G. Manikandanb , V. Thanikachalama, K. Gokula Krishnana
aDepartment of Chemistry, Annamalai University, Annamalai Nagar-608 002, Tamil Nadu, India.
bChemistry Section (FEAT), Annamalai University, Annamalai Nagar-608 002, Tamil Nadu, India.
Graphical Abstract
Corresponding Author: Tel.: +91-9994325507, E-mail: phdmani@gmail.com (G. Manikandan)

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Synthesis, spectroscopic investigation and theoretical studies of
2-((E)-(2-(2-cyanoacetyl)hydrazono)methyl)-4-((E)-
phenyldiazenyl)phenyl methyl carbonate
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A. Arokiasamya, G. Manikandanb , V. Thanikachalama, K. Gokula Krishnana
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aDepartment of Chemistry, Annamalai University, Annamalai Nagar-608 002, Tamil Nadu, India.
bChemistry Section (FEAT), Annamalai University, Annamalai Nagar-608 002, Tamil Nadu, India.
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ABSTRACT
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Synthesis and computational optimization studies have been carried out by Hartree–
Fock (HF) and Density Functional Theory (DFT–B3LYP) methods with 6–31+G(d, p)
basis set for 2-((E)-(2-(2-cyanoacetyl)hydrazono)methyl)-4-((E)-phenyldiazenyl)phenyl methyl
carbonate (CHPMC). The stable configuration of CHPMC was confirmed theoretically by
potential energy surface scan analysis. The complete vibrational assignments were performed
on the basis of total energy distribution (TED) analysis. The vibrational properties studied by
IR and Raman spectroscopic data complemented by quantum chemical calculations
support the formation of intramolecular hydrogen bond. Furthermore, the
UV-Vis spectra are interpreted in terms of TD-DFT quantum chemical calculations. The
shapes of the simulated absorption spectra are in good agreement with the experimental data.
The comparison between the experimental and theoretical values of FT-IR, FT-Raman
vibrational spectra, NMR (1H and 13C) and UV-Vis spectra have also been discussed.
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Keywords: cyanoacetyl; hydrazone; diazenyl; methyl carbonate; FT–Raman
Corresponding Author: Tel.: +91-9994325507, E-mail: phdmani@gmail.com (G. Manikandan)

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INTRODUCTION
Aromatic and hetero aromatic azo compounds constitute the largest and the most
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diverse group of synthetic dyes with application not only as textile colorants but in many
other industrial fields such as textile, fiber and biomedical studies. Besides, in high
technological areas such as laser, liquid crystalline display boards, electro-optical devices and
ink-jet printers [1–6] are advanced applications. Generally, organic carbonates are important
precursors and have unique applications in industry [7–9] and biological/medicinal fields
[10]. They are useful synthetic intermediates [11–13]. Furthermore, hydrazones [14] are important
molecules containing highly reactive azomethine group (-CO-NH-N=CH-) and are useful in
drug development. Hydrazides [15] and their derivatives show a wide range of biological
activities such as antibacterial and tuberculostatic properties. Moreover, hydrazine and acyl
hydrazine moieties [16–18] are also found to be the most important pharmacophore in many
anti-inflammatory, anti-nociceptive and anti-platelet drug molecules. Cyanoacetyl
hydrazones exhibit antitumor activity [19,20] against several cell lines. Literature survey
reveals that DFT calculations and experimental studies of CHPMC have not been reported so
far. Therefore, the present work deals the synthesis of title compound and analysis of
experimental FT–IR, FT–Raman, NMR (1H and 13C) and UV-Vis spectra. Further,
comparison of experimental with corresponding computational values which carried out by
HF and B3LYP methods with 6–31+G(d, p) as basis set.
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EXPERIMENTAL
2.1
Synthesis of CHPMC
2-((E)-(2-(2-cyanoacetyl)hydrazono)methyl)-4-((E)-phenyldiazenyl)phenylmethyl
carbonate (CHPMC) was synthesized by a three step procedure as shown in Scheme 1.
The first and second step compounds were synthesized by literature methods [21, 22].
The third step is the synthesis of CHPMC is as follows: A mixture of 2-formyl-4-
(phenyldiazenyl)phenyl methyl carbonate (FPMC) [23] and cyanoacetic hydrazide (3 mmol)
in ethanol (10 mL) was refluxed for 3–6 h. The progress of the reaction was monitored by
thin layer chromatography (TLC) method. After completion of the reaction, the solid product
separated by filtration and washed well with water. The pure sample was obtained by
recrystallization from 1:1 mixture of ethanol and ethyl acetate.
2.2
Spectral measurements
The melting point was measured in open capillary and is uncorrected. FT–IR
spectrum was recorded on a Thermo Nicolet iS5 FT–IR spectrometer in the range of 500 to

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4000 cm-1 by ATR with number of scans equals 16, at Annamalai University, Annamalai
Nagar, India. FT–Raman spectrum was recorded on a Bruker: RFS 27 spectrometer at SAIF,
Indian Institute of Technology (IIT), Chennai (Tamil Nadu, India) and the spectral features
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are reported in wave number (cm-1). H NMR spectrum was recorded on a Bruker 400 MHz
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spectrometer and 13C NMR spectrum was recorded on a Bruker 100 MHz spectrometer at
Annamalai University, Annamalai Nagar, India. Chemical shift values are reported in parts
per million (ppm) from tetramethylsilane (TMS) as internal standard. The UV-Vis spectra of
the title molecule were taken in the range of 200-800 nm using Shimadzu 1650 PC recording
spectrometer.
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2.3
Computational details
Molecular quantum chemical calculations have been performed with the GAUSSIAN
09 program [24]. The ground state optimisations of title compound have been carried out
using Hartree–Fock (HF) and DFT with Becke-3-Lee-Yang-Parr (B3LYP) exchange-
correlation function [25,26] in combination with 6–31+G(d, p) basis sets. The simulated IR
spectrum was analysed by GAUSSVIEW and VEDA 4 (Vibrational Energy Distribution
Analysis) [27,28] program to assign vibrational frequencies with high degree of accuracy. For
electronic excited state calculation, TD-DFT/B3LYP method has been employed with the
same basis set considered for ground state optimization. Molecular electrostatic potential of
the molecule have also been presented to view electrophilic and nucleophilic reactive sites
[29, 30]. The TD-DFT method with B3LYP/6-31+G(d,p) basis set is employed to obtain UV-
Vis spectrum, electronic transitions, vertical excitation energies, absorbance, and oscillator
strength of the studied compound. The frontier molecular orbitals (FMOs), such as HOMO
and LUMO, energies are obtained also by TD-DFT approach [31].
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RESULTS AND DISCUSSION
3.1
Potential energy surface scan analysis
The conformational analysis of CHPMC was carried out through the potential energy
surface scan analysis (PES) for determining the most stable geometry have low energy by
B3LYP/6–31+G(d, p) level. The preliminary search of the low energy structure was
performed by different dihedral angles C3–C4–N12–N13 (azo), C31–N33–N34–H35
(hydrazone moiety) [32] and C19–C21–O23–C24 (carbonate moiety) which are relevant
coordinate for conformational flexibility within the molecule. During this analysis, all the
geometrical parameters have been simultaneously relaxed with the above dihedral angles
which are varied in steps of 10 º from 0 º to 360 º. The potential energy barriers with
corresponding geometrical structures are shown in Fig. 1. From Fig. 1, rotation through

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the dihedral angle of C3–C4–N12–N13 gave different geometrical structures (Fig. 2 a-d)
especially, geometrical structure a is attained minimum energy which is equal to -1269.6826
Hartree corresponding scan coordinates at -0.52 º and 359.48 º and the dihedral angle
C19–C21–O23–C24 is attained minimum energy which is equal to -1269.5850 Hartree
corresponding scan coordinates at -108.06º and 251.94 º and the corresponding geometrical
structure is g. Comparing the energy of the geometrical structures a to g in Fig. 2, the
optimized geometrical structure of CHPMC is g and phenyl diazenyl phenyl moiety having
E-form configuration [33] which is shown in Fig. 3.
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3.2
Molecular geometry
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The calculated structural parameters such as bond lengths, bond angles and dihedral
angles have been compared with the crystal structure of azo compounds available in the
literature [34]. The calculated structural parameters depicted in Table 1. It is observed from
the Fig. 3, the basic azo dye unit in CHPMC is planar and aromatic in nature due to the
continuous delocalization of electrons in the phenyl rings through azo group. From
Table 1, the variations in the C–C and C–N bond lengths of FPMC which is the parent
compound of CHPMC and the corresponding literature values [23] are C3–C4
(1.407/1.407/1.390 Å), C4–C5 (1.403/1.403/1.402 Å), C4–N12 (1.418/1.418/1.428 Å),
N12–N13 (1.258/1.258/1.259 Å), N13–C14 (1.418/1.419/1.425 Å), C14–C15
(1.397/1.397/1.381 Å), C14–C16 (1.407/1.406/1.412 Å), C17–C21 (1.410/1.412/1.415 Å)
and C17–C31 (1.480/1.464/1.459 Å) are ascribable due to substituent effect, electronegativity
and lone pair of electrons present in the molecule. The comparison of theoretical C–C, C–N
and N=N bond lengths values of phenyl (1) ring were found to be significantly same for
FPMC and CHPMC. From the results of Table 1, there is no significant effect present in
phenyl (1) ring and significant effect present in phenyl (2) ring due to the substitution of
cyanoacetic hydrazide group in the side chain of the phenyl (2) ring of CHPMC.
3.3
Vibrational analysis
CHPMC has 42 atoms which belongs to C1 symmetry and possess 120 normal modes
of vibrations. All the 120 modes of vibrations are distributed as 41 stretching, 40 bending, 33
torsion and 6 out–of–plane vibrations. The experimental and calculated scaled frequencies as
well as the TED values are listed in Table 2. The calculated frequencies are found to be very
close to the experimental values. The mean percentage deviations of the calculated
frequencies from the experimental ones are about 1.0–2.0 %. The experimental FT–IR and
FT–Raman spectra with the corresponding theoretically simulated ones are shown in Figs.4 and 5.

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3.3.1 C=O vibrations
The carbonyl stretching vibrations are expected in the region between 1715-1680 cm-1
[35,36]. In the studied compound, the C=O stretching band of carbonate was observed at 1767
and 1763 cm-1 in the experimental FT-IR and FT-Raman spectra and hydrazone C=O
stretching band observed at 1699 and 1666 cm-1 which are shown in Table 2. From the
B3LYP (6-31+G/d,p) calculation, C=O stretching band was observed at 1780 cm-1 (mode no.
104) for carbonate and 1688 cm-1 for hydrazone (mode no. 103) which are very close to the
experimental FT-IR and FT-Raman values. These wave numbers are shifted from expect one,
due to the substitution of carbonate and hydrazone para and meta positions, respectively.
3.3.2 C–C and C=C vibrations
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The six ring carbon atoms undergo coupled vibrations therefore actual positions of
these modes are not determined so much by the nature of the substituent but by the form of
substitution around the ring [37]. The coupled vibrations are usually occurring in the region
1400–1625 cm-1 [38]. In the FT–IR spectrum, C–C vibration bands are observed with variable
intensities at 1536, 1556, 1585 and 1601 cm-1. FT–Raman bands were observed at 1530, 1576,
1592 and 1603 cm-1. The theoretically computed FT–IR frequencies from
B3LYP/6–31+G(d, p) method are predicted at 1318, 1321, 1552, 1574, 1589 and 1596 cm-1
(mode nos. 85, 86 and 98–101) and most of the theoretical modes of vibrations are closed to
the experimental data.
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3.3.3 C–H vibrations
The C–H stretching vibrations in aromatic ring characteristically appear above 3000
cm-1 and are typically exhibited as a multiplicity of weak to moderate bands [34]. From
B3LYP/6–31+G(d, p) method, 42 C–H vibration modes occurred which are distributed as
14 stretching, 14 bending and 14 torsion vibrations, respectively. The C–H stretching
frequencies of two phenyl rings having nine modes are 111 to 119 at the region
of 3184–3234 cm-1. The aromatic C–H in–plane bending vibrations are observed at 1092,
1142, 1433, 1455 and 1470 cm-1 and the corresponding mode nos. are 70, 73, 92, 95 and 96,
respectively. In experimental FT–IR and FT-Raman spectra, the strong bands occur in the
region 3430–3027 and 3200–3080 cm-1 which have been assigned as C–H asymmetric
stretching vibrations of aromatic phenyl rings. The C–H in–plane bending harmonic
vibrations occurred at around 1479 cm-1 (mode no. 96) in FT–IR spectrum whereas at 1464
cm-1 in FT–Raman spectrum which are showed in good agreement with medium and strong
FT–IR and FT–Raman bands.

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3.3.4 Methyl group vibrations
The asymmetric stretching vibrations of methyl and methylene groups (–CH3 and
–CH2) are expected to appear at about 2980 cm-1 and symmetric stretching vibrations around
2870 cm-1 [34]. In computed FT–IR spectrum of C–H stretching vibrations of carbonate
CH3 group were observed at 2966, 2972, 2983, 3023 and 3048 cm-1 (mode nos. 106 to 110).
In the experimental FT–IR spectrum, C–H stretching vibrations of methyl groups were
observed at 2820, 2826, 2880 and 2926 cm-1, in FT-Raman at 2831, 2940, 2968 and
3023 cm-1 were observed.
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3.3.5 Azo chromophoric group (–C-N=N-C-) vibrations
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Azo chromophoric group contains two bonds i.e., C-N and N=N, each has its own
well known characteristic vibrational wave number. The N=N stretching vibration has a very
characteristic and intense band in the Raman and difficult to observe in IR spectrum due to its
symmetry [39]. This molecule has two unequivalent C-N parts causes change in dipole
moment therefore the N=N stretching is IR active. Literature survey reveals that the bands
occurring between 1380 and 1450 cm-1 corresponds to the N=N stretching vibrational
frequencies of azo group [40,41]. In our compound, the stretching frequency of N=N
(N12–N13) is observed at 1491, 1489 and 1499 cm-1 (mode no: 97) in theoretical,
experimental FT–IR and FT–Raman spectra, respectively and C31=N33 (C=N) stretching
frequency at 1615, 1610 and 1630 cm-1 (mode no. 102) in theoretical, experimental FT–IR
and FT–Raman spectra, respectively. Furthermore, C41≡N42 (C≡N) stretching frequency
observed at 2265, 2265 and 2277 cm-1 (mode no. 105) in theoretical, experimental FT–IR and
FT–Raman spectra, respectively. In addition the N34–H35 stretching frequency is observed
at 3431, 3435 and 3469 cm-1 (mode no. 120) in theoretical, experimental FT–IR and
FT–Raman spectra, respectively. FT-IR spectral data clearly show that intramolecular
hydrogen bond interactions involving the N-H donors. Medium intensity absorption at
3121 cm-1 is found in the FT-IR spectrum of the studied molecule, which can associated with
the ν(NH) stretching mode. Data obtained by DFT calculations indicate that the formation of
the intramolecular N-H---O=C hydrogen bond produces a red shift to a strong interaction of
the ν(NH) as computed with other amide ν(NH) stretching [42]. These shift in wave numbers
and intensity depending on the neighbouring groups, conjugation effects, H-bonding and
molecular tautomerism. The correlations between the experimental and theoretical values are
good in agreement.

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3.4
NMR spectral analysis
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The H and C chemical shift calculations of CHPMC have been carried out by HF
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and B3LYP methods with 6–31+G(d, p) basis set [43]. The comparisons of experimental and
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computational chemical shift values are listed in Table 3. In H NMR (Fig. 6) spectrum,
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three signals observed in up field region, one at 3.957 (s) ppm with three protons integral
corresponds to H28, H29 and H30 atoms, respectively and another at 4.033 and 4.037 (d)
with two protons integral corresponds to H39 and H40 atoms, respectively. In HOMO COSY
(Fig. S1) and HSQC (Fig. S2) NMR spectra, the signal observed at 11.914 (s) ppm
corresponds to H35 atom which is N-H proton. The signals at 8.257 (s) ppm and 8.406
corresponds to H32 and H18 atoms, respectively. The signals at 7.404 (dd) and 7.987 (m)
ppm corresponds to H22 and to H20 atoms, respectively. Besides, signals at 7.933 and 7.953
ppm correspond to H9 and H10 atoms, respectively. These chemical shift values were found
to be good agreement with the computed values. The root mean square (RMS) value of
experimental with theoretical (B3LYP/6–31+G(d, p) basis set) 1H chemical shifts is found to
be 0.99.
In 13C NMR (Fig. 7), spectral signals are assigned based on HSQC and HMBC
spectra which are shown in Figs. S2 and S3. The aromatic carbons of CHPMC signals
observed at 122.50, 128.76, 139.50, 126.38, 123.37 and 122.38 ppm, respectively (Table 3).
The shielded signals observed at 23.91 and 55.51 ppm are assigned to C38 and the carbonate
methyl carbon C27, respectively. The deshielded signals for carbonyl carbons C36 and C24
appeared at 163.99 and 152.79 ppm, respectively. The signal at 151.70, 150.29 and 149.75
ppm are assigned to C4, C14 and C21 which are more deshielded than other ring carbons due
to N12–N13 and O23–C24–O25–O26 bonds. The RMS value of experimental with
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theoretical (B3LYP/6–31+G(d, p) basis set) C chemical shifts is found to be 0.983. From
the RMS values, the experimental (1H and 13C) chemical shift values are good agreement
with the theoretical (B3LYP/6–31+G(d, p) basis set) chemical shift values. Besides, the
experimental chemical shift values (1H and 13C) are very close to the literature value [43].
3.5
NBO analysis
From the NBO results, the π–electron delocalization is maximum around the
C14–C15 and C17–C21 bonds to the π*(C16–C19) and π*(C17–C21) of the phenyl (2) ring
which has higher ED value equals 0.2845 eV with the stabilization energies equal
16.55 and 18.25 kcal/mol.
Another interaction energy between the filled π(C4–C5) and π(C14–C15) bond orbital of
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19.28 kcal/mol, respectively. Besides, the interaction energy between the filled π(N12–N13)
bond orbital and the empty π*(C4–C5) and π*(C14–C15) orbital of phenyl (1) ring and
phenyl (2) ring occurs at 9.95 and 10.58 kcal/mol, respectively. Therefore the lone pair
electrons of the azo group delocalized between two phenyl rings and the azo group being
coplanar with the phenyl (2) ring.
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The most important interaction energy, related to the resonance in the molecule is an
electron donation from lone pair electrons (n) to the anti–bonding acceptor π*(C–C) i.e., n–π*
interactions [44] of the phenyl rings which denotes the delocalization or extension of
conjugation present in the molecule. In this compound, lone pair (n) electron donation from
LP(1)O23 to the anti–bonding acceptor π*(C17–C21) of the phenyl (2) ring is equivalent to
7.13 kcal/mol which is lower than LP(2)O23 to anti–bonding acceptor σ*(C24–O25) which is
almost equal to 18.88 kcal/mol. Furthermore σ*(C24–O25) to π*(C24–O25) results in a
stabilization energy value of 80.68 kcal/mol. Therefore electrons of LP(2) O23 are preferred
to delocalization over C24–O23 and not for phenyl (2) ring. Hence the extension of
conjugation is absent from phenyl (2) ring to C24-O23 atom which is shown in Fig. 8 and the
values are tabulated in Table S1.
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3.6
HOMO–LUMO analysis
The HOMO and LUMO are important quantum chemical parameters to determine the
molecular interaction of one species with other species and to characterize the chemical
reactivity, global hardness, softness and kinetic stability of the molecule etc. [45]. The 3D
plots of HOMO, LUMO and the energy gap have been calculated using B3LYP/6–31+G(d, p)
method. According to Fig. 8, the HOMO orbitals are delocalized over the nitrogen atoms and
the carbon atoms of C3, C4, C14 and C15 while the side chains of phenyl rings the charge
distribution is localized. Moreover, a small energy difference in between HOMO and LUMO
equals 2.355 eV explains the eventual charge transfer interactions occurring within the
molecule. ∆E value is very small when compared with parent compound [23] due to
substitution of cyanoacetic hydrazide influences HOMO and LUMO energy gap.
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Due to high accuracy and low computational cost of TD-DFT, it has been popularised
for theoretical investigation of electronic spectra of molecules. The nature of transitions in the
observed UV-Visible spectrum of CHPMC has been studied by the time dependent density
functional theory (TD–DFT) with Gaussian 09 software program. The experimental and
simulated UV-Visible absorption spectra of CHPMC in different solvents are shown in
Fig. 9. The vertical excitation energies, oscillator strength (f) and transition wavelength along

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with assignments are presented in Table 4. The experimental UV-Visible wavelength range
observed at 344.5–348 nm and 368–372.5 nm and corresponding theoretically computed
wavelength showed in the range at 346-349 nm, 367-368 nm and 476-480 nm, respectively
.These excitations correspond to (n– σ*) electronic transition. The absorption peak at 344.5
nm in ethanol has highest absorbance of 0.646 a.u., which corresponds to 349 nm wavelength
and oscillator strength is 0.2870 associated with HOMO-2 to LUMO transition having
theoretically 60% contribution. As evident from Fig. 10, HOMO-2 electron density is
localized over oxygen of hydrazone moiety. Transitions observed in the ranges 344.5–348 nm
qualitatively are in good agreement with theoretical range of 346-349 nm. The other
important transition was observed ranges at 368–372.5 nm with absorbance 0.434 a.u. which
is good in agreement with calculated ranges 367-368 nm. The molecular orbitals involved in
major contribution are HOMO to LUMO (33%).
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Using HOMO and LUMO orbital energies, the ionization potential (Ip), electron
affinity (A), electronegativity (χ), hardness (η) and softness (σ) can be expressed as:
Ip= -EHOMO
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A = -ELUMO
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χ = (IP + A)/2
σ =1/η
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which are found by Koopman’s theorem [45] and the values are given in the Table 5.
The hardness of the molecule is 1.17 eV and believed to be soft or chemically active.
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3.7
Mulliken population analysis
The Mulliken charge distributions over the atoms suggest that the charge density, the
donor and acceptor behaviours of atoms in the molecule [46,47]. The net Mulliken atomic charge
distribution is shown in Fig. 11 and the values of are listed in Table 6 which are provides the
atomic charge density or an orbital density on individual atom of CHPMC. From the Table 5,
C14 carbon atom attached to the nitrogen atom (N13) has been attained highest negative
charge and behaved as electron acceptor. The large accumulation of positive charge is found
to be on carbon C16 and C17 atoms than the other atoms and behaved as electron donor.
3.8
Molecular electrostatic potential
To predict the reactive sites for electrophilic and nucleophilic attacks of CHPMC were
calculated by molecular electrostatic potential (MEP) [48,49]. Each molecule is encompassed
by a characteristic three dimensional surface corresponding to contour of 0.002 a.u.
isodensity surface. From the MEP analysis of Figs. 12 and 13, the electron density surface

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mapped with electrostatic potential surface (ESP) range is -1.115 to 1.115 and ESP mapped
to the total density range is -3.238 x 10-2 to 3.238 x 10-2. Furthermore, from the Figs. 12 and 13,
the red region represents to most negative electrostatic potential (electrophilic attack) which
is shown in O23, O25, O37 and N41. Blue region represents to most positive electrostatic
potential (nucleophilic attack) and green region represents to zero potential.
6
4
CONCLUSION
7
8
CHPMC was synthesized and characterized by various spectroscopic methods. The
experimental and theoretical (DFT) studies were investigated, related on the structural UV-
Vis, NMR and vibrational (FT-IR and FT-Raman) spectra of CHPMC. The optimized
geometrical parameters (bond lengths, bond angles and dihedral angles) were determined by
using B3LYP/6-31+G(d, p) level of theory. The vibrational properties of the studied
compound are obtained by experimental and theoretical quantum chemical methods with
their PED. The stable configuration of the compound has been studied. CHPMC has
intramolecular charge transfer which is confirmed by HOMO-LUMO analysis, the difference
in HOMO and LUMO energies support the charge transfer interactions occur within the
molecule. The UV-Vis spectra were measured in gas phase and different solvents. MEPs and
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
1
13
Mulliken atomic charges of the molecule presented. H and C NMR theoretical results are
showed well agree with their tentative data.

11
ACCEPTED MANUSCRIPT
1
2
3
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1
2
Captions for Scheme and Figures
Scheme 1. Synthesis of CHPMC.
3
Fig. 1. Potential energy surface scan of CHPMC with different scan coordinates.
Fig. 2. Different geometrical structures of CHPMC.
4
5
Fig. 3. Optimized structure of CHPMC.
6
Fig. 4. a) Experimental FT–IR and b) Theoretical FT–IR spectra of CHPMC.
Fig. 5. a) Experimental FT–Raman and b) Theoretical FT– Raman spectra of CHPMC.
Fig. 6. 1H NMR spectrum of CHPMC.
7
8
9
Fig. 7. 13C NMR spectrum of CHPMC.
10
11
12
13
14
15
16
Fig. 8. HOMO–LUMO plot by B3LYP method.
Fig. 9. (a) Experimental UV-Visible and (b) Theoretical UV-Vis spectra of CHPMC.
Fig. 10. Frontier molecular orbital of CHPMC.
Fig. 11. Mulliken charge distribution of atoms.
Fig. 12. Electron density surface mapped with total density of CHPMC.
Fig. 13. Electrostatic potential surface mapped with total density of CHPMC.

ACCEPTED MANUSCRIPT
Table 1
Selected structural parameters for CHPMC.
Bond
length (Å)
Expt.
(Ref. 21)
Expt.
Expt.
(Ref. 21)
HF
B3LYP
Bond angle (º)
HF
B3LYP
Dihedral angle (º)
HF
B3LYP
(Ref. 21)
118.8
121.6
117.3
119.7
119.2
121
C3–C4
1.394
1.386
1.421
1.218
1.421
1.378
1.398
1.383
1.476
1.471
1.135
1.407
1.403
1.418
1.258
1.419
1.397
1.406
1.412
1.464
1.464
1.161
1.39
C3–C2–H8
119.6
120.8
119.9
120.1
119
119.7
121.2
119.3
120.1
118.5
121.4
119.8
115.5
125.1
127.3
115.7
C2–C1–C6–H11
H7–C1–C6–H11
C1–C2–C3–C4
179.9
0.047
-0.028
-0.274
-179.8
179.5
-0.091
-4.88
180
C4–C5
1.402
1.428
1.259
1.425
1.381
1.412
1.415
1.459
C2–C3–H9
0.016
-0.011
0.001
-179.9
180
C4–N12
N12–N13
N13–C14
C14–C15
C14–C16
C17–C21
C17–C31
C38–C41
C41–N42
C4–C3–H9
0.6
-1
C4–C5–C6
C2–C3–C4–C5
C4–C5–H10
C6–C5–H10
C1–C6–C5
C2–C3–C4–N12
H9–C3–C4–C5
179
121
119.8
115.6
124.3
126.1
117
121.9
117.1
124.6
H9–C3–C4–N12
C3–C4–N12–N1C3
C5–C4–N12–N13
C14–C16–C19–C21
C14–C16–C19–H22
0.069
-0.52
179.6
0.625
-179.1
N13–C14–C15
N13–C14–C16
O25–C24–O26
C24–O26–C27
177
-3.7
-1.1
175.5
0.308
-179.8
Expt. – Experimental; Ref. 21- Reference [21]

ACCEPTED MANUSCRIPT
Table 2
Experimental and calculated vibrational spectral values of CHPMC.
Observed Freq.
Scaled
Intensity
IR
(cm-1)
IR
Mode
No
Reduced Force Vibrational Assignments
Freq.
Mass
const. with TED ≥ 10%
(cm-1)
Raman
Raman
6.1
τC5C4N12N13 (35) +
τC16C14N13N12 (46)
1
2
3
4
17
22
31
34
0.3
4
0
τC31N33N34C36 (22) +
τC41C38C36N34 (17)
2.1
3.2
0.2
3.2
2.8
5.1
8.5
5.8
6.9
0
τC17C21O23C24 (18) +
τC4N12N13C14 (12)
0
βC16C21C19 (10) +
βC31N33N34 (16)
0
βC36N34N33 (12) +
τC41C38C36N34 (10) +
τC17C31N33N34 (14) +
5
45
0.3
2.2
7
0
τC38C36N34N33 (15)
τC31N33N34C36 (12) +
6
7
46
60
3.7
6
2.5
2.5
5.4
5.6
0
0
τC17C21O23C24 (15) +
τC41C38C36N34 (27)
τC15C17C31N33 (29) +
τC17C21O23C24 (16) +
τC41C38C36N34 (10)
8
9
64
72
2.6
1.8
1.1
0.9
4.4
4.5
0
0
τC21O23C24O26 (41)
τC21O23C24O26 (15) +
τC4N12N13C14 (13)
τC17C21O23C24 (14) +
τC38C36N34N33 (13)
10
11
83
0.8
0.8
0.7
0.7
5.3
1.4
0
0
τH28C27O26C24 (10) +
τH29C27O26C24 (26) +
τH30C27O26C24 (22) +
τC27O26C24O23 (13)
101
βC21O23C24 (17) +
τC5C4N12N13 (27) +
τC16C14N13N12 (20)
12
109
0.5
1.3
5.9
0
τC17C15C21C19 (11) +
τC38C36N34N33 (14) +
ΓC31C15C2117 (10)
13
14
15
122
134
148
3.9
4.1
3.5
2.4
3.4
0.7
5.1
7.5
5.1
0.1
0.1
0.1
βC36C38C41 (47) +
βC38C36N34 (13)
βC21C17C31 (13) +
τH28C27O26C24 (10) +
τC27O26C24O23 (24)
τC15C17C31N33 (16) +
τC27O26C24O23 (13) +
ΓC31C15C2117 (10)
16
169
14.3
22.4
4
0.1
17
18
19
184
195
209
5.3
8.6
3.2
5.5
7.3
4.8
6
0.1
0.1
0.2
τC3C2C4C5 (85)
6
τC27O26C24O23 (20)
τC16C19C17C21 (72)
7.4
βC17C31N33 (10) +
βC16C21C19 (15) +
20
232
2.4
2.3
6.7
0.2

ACCEPTED MANUSCRIPT
βC3C4N12 (12)
βC24O26C27 (11) +
τC3C2C4C5 (31)
21
22
23
270
280
307
2.5
7.7
6
2.4
2.9
4.8
5.5
4.8
5.9
0.3
0.2
0.4
βC24O26C27 (31)
βC24O26C27 (13) +
βC38C36N34 (13)
βC38C36N34 (12) +
τC17C31N33N34 (14)
24
25
326
345
7.3
3.4
0.8
2.5
6.1
5.6
0.4
0.4
τC1C6C4C5 (26) +
τH10C5C6C1 (15)
βC38C41N42 (51) +
τH39C38C41N42 (13) +
τC36C3841N42 (14)
26
27
349
376
0.6
4.8
3.5
2.2
3.3
5.2
0.3
0.5
τC14C16C21C19 (30) +
τC16C19C17C21 (10) +
ΓN13C14C1615 (12)
28
29
30
414
402
405
442
26.7
0.5
2.5
0.1
8.8
7.7
3
0.8
0.3
0.9
βC19C21O23 (36)
τC1C6C4C5 (46) +
τC1C6C2C3 (23)
426
447
5.9
7.1
βO23C24025 (12)
βC38C36N34 (12) +
τH40C38C41N42 (11) +
τC36C3841N42 (21) +
ΓO37C38N34C36 (11)
31
448
6.2
1.5
4.6
0.6
τC16C19C17C21 (15) +
ΓO23C17C19C21 (12)
32
33
34
35
459
471
484
501
518
1.7
10.3
5.1
37
5.6
3.8
6.1
3.4
3.8
0.5
0.9
0.5
0.7
11.1
3.9
βN34C36O37 (25)
τC1C6C2C3 (17) +
ΓN12C3C5C4 (28)
7.5
τH35N34N33C31 (13)
βC16C21C19 (15) +
βC3C4N12 (10) +
36
554
540
74.2
5.2
3.7
0.7
τH35N34N33C31 (11)
βO23C24025 (15) +
βC2C1C6 (12)
37
38
39
560
598
604
2.8
1.8
1.1
9.1
6.4
4.8
6.3
1.3
1.1
1.5
ΓC31C15C2117 (21) +
ΓN13C14C1615 (21)
587
606
2.3
βC4C5C6 (42) +
βC2C3C4 (35)
15.6
40
41
621
635
10.1
1.4
5
3.9
4.8
1
βC19C21O23 (28)
βO23C24O26 (14)
6.2
1.2
τH35N34N33C31 (37) +
ΓO37C38N34C36 (29)
42
655
699
655
121.7 2.9
2.1
0.6
βO23C24025 (10) +
βC17C21C19 (15) +
βC2C1C6 (16)
43
658
0.7
8.8
0
7.3
2
τH7C1C2C3 (20) +
τH9H3C2C1 (14) +
τH10C5C6C1 (16) +
τC1C6C4C5 (18) +
τC3C2C4C5 (18)
44
671
37.4
2
0.6

ACCEPTED MANUSCRIPT
τH29C27O26C24 (23) +
βC21O23C24 (37) +
βC2C1C6 (11)
45
716
3.6
6.4
6
1.9
46
47
720
734
36
1.6
5
8.9
4.7
2.9
1.6
ΓO25O23O26C24 (72)
ΓO25O23O26C24 (14) +
ΓO23C17C19C21 (10)
1.9
τH7C1C2C3 (20) +
τH8C2C3C4 (22) +
τH11C6C1C2 (19) +
ΓN12C3C5C4 (19)
48
756
39.7
2.9
1.8
0.6
νC17C21 (12) +
βO23C24025 (10)
49
50
777
797
8.1
4.3
33
4.8
4.9
1.8
2
28.7
νC36C38 (20)
τH8C2C3C4 (25) +
τH9H3C2C1 (25) +
τH10C5C6C1 (25) +
τH11C6C1C2 (24)
51
826
0
0.3
1.3
0.5
52
53
828
840
3.9
4
5.3
1.6
2.3
0.7
βC31N33N34 (11)
τH20C16C19C21 (35) +
τH22C19C21C17 (30) +
ΓO23C17C19C21 (14)
867
901
869
24.3
3.2
54
55
884
889
9.4
1.7
8.5
1.5
4.9
0.8
2.5
τH18C15C17C21 (65)
νC3C4 (12) + βC4N12N13
(11) + βC14N13N12 (15)
12.2
τH39C38C41N42 (11) +
τC36C3841N42 (15)
56
57
911
912
11.9
53.9
4.2
4.6
2.7
4.1
1.4
2.2
νO26C24 (12) + νO26C27
(13)
τH7C1C2C3 (29) +
τH9H3C2C1 (24) +
τH10C5C6C1 (31)
58
915
5.6
0.2
1.4
0.8
59
60
934
931
944
1.4
2
0.9
21
3.7
2.7
2
νC38C41 (65)
βC16C19C21 (10) +
τH32C31N33N34 (23)
1.5
τH11C6C1C2 (14) +
τH20C16C19C21 (22) +
τH22C19C21C17 (19)
61
958
0.2
1.2
1.4
0.8
τH9H3C2C1 (10) +
τH11C6C1C2 (16) +
τH20C16C19C21 (20) +
τH22C19C21C17 (18)
62
63
64
958
963
972
0.1
9.8
0
1.2
1.4
1.8
1.3
0.8
1.1
0.8
11.4
1.3
τH32C31N33N34 (56)
τH7C1C2C3 (21) +
τH8C2C3C4 (27) +
τH11C6C1C2 (12) +
τC1C6C2C3 (26)
νC3C4 (10) + βC4C5C6
(20) + βC2C1C6 (20) +
βC2C3C4 (20)
65
980
978
2.4
213.4
6
3.7
66
67
1005
1038
9.3
12
25.5
29.4
2.1
8.5
1.3
5.8
νC1C6 (25) + νC1C2 (31)
νO23C24 (22) + νO26C27
(54)
1019

ACCEPTED MANUSCRIPT
νC2C3 (14) + νC5C6 (19) +
βH7C1C2 (11) + βH9C3C2
(16) + βH10C5C6 (15)
68
1050
1093
1062
7.6
24.5
1.5
1.1
νN33N34 (49) +
βN34C36O37 (12)
69
70
71
1067
1092
1129
12.7
70.1
22.2
78.9
4.4
1.5
1.7
3.2
1.1
1.3
βH20C16C19 (37) +
βC16C19C21 (10)
1093
891.2
2508.6
νN12C4 (13) + βH9C3C2
(12) + βH10C5C6 (18)
βH28C27H30 (15) +
βH28C27H29 (13) +
τH28C27O26C24 (39) +
τH29C27O26C24 (10) +
τH30C27O26C24 (21)
72
73
1136
1142
4
3.5
21
1.3
1.1
1
νC1C2 (10) + βH7C1C2
(37) + βH8C2C3 (19) +
βH11C6C1 (14)
1142
1145
5.8
0.9
νN13C14 (11) + βH11C6C1
(15) + βH18C15C17 (14)
74
75
1137
1158
1146
1156
13.8
58.7
194.4
74.4
1.4
1.2
1.2
1.1
βH39C38C41 (58) +
τH40C38C41N42 (11)
βH29C27H30 (19) +
τH29C27O26C24 (32) +
τH30C27O26C24 (23)
76
77
1172
1192
0.8
3.4
1.5
2.7
1.3
2.4
νN12C4 (29) + βH8C2C3
(11)
1187
1190
15.5
1734.1
νO26C24 (10) + νO23C24
(23) + νO23C21 (28
78
79
80
1194
1219
1230
711.1 7.8
4.9
5.3
5.3
4.4
5
288
63
199.1
νO26C24 (30)
νC19C21 (10) + νC15C17
(11) + νN13C14 (17)
711.2
5
βH18C15C17 (22) +
βH20C16C19 (11) +
βH22C19C21 (30)
81
82
1237
1261
1275
1236
1263
1281
1239
1265
19.8
9
47
1.5
1.5
1.5
1.5
βH39C38C41 (12) +
τH39C38C41N42 (28) +
τH40C38C41N42 (30)
4.5
βH8C2C3 (14) + βH9C3C2
(19) + βH10C5C6 (25) +
βH11C6C1 (14)
83
84
85
1292
1302
1318
2
317.4
1.5
3.8
6.2
1.5
4.1
6.8
νN34C36 (47) + νC36C38
(14) + βN34C36O37 (12)
332.7 58.8
νC2C3 (17) + νC1C6 (15) +
νC5C6 (11) + νC1C2 (11) +
νC4C5 (13) + νC3C4 (12)
1309
8.4
98.5
νC16C19 (19) + νC14C15
(15) + νC15C17 (11) +
νC17C21 (17)
86
1321
25.9
156.4
9
9.9
87
88
89
1367
1383
1401
1366
1380
1412
1339
1390
1412
22.8
36.5
18.7
101.5
268.3
11.3
1.7
3.3
1.1
1.9
4.1
1.4
βH32C31N33 (51)
νC15C17 (20) +
βH35N34NC2 (13)
βH39C38H40 (87)

ACCEPTED MANUSCRIPT
βH28C27H30 (55) +
βH28C27H29 (21)
90
91
1426
1428
33.4
7.5
2.5
1.2
1.5
1.5
1.9
βH35N34N33 (61) +
βH32C31N33 (14)
134.8
νC5C6 (15) + βH7C1C2
(23) + βH8C2C3 (12) +
βH11C6C1 (10)
92
93
1433
1434
8.4
1426.2
11.3
2.4
1.1
3.2
1.4
βH28C27H30 (20) +
βH28C27H29 (52) +
τH28C27O26C24 (19)
1438
18.7
βH29C27H30 (71) +
τH30C27O26C24 (10)
94
95
1444
1464
1446
1455
9.3
18.4
1.1
2.5
1.4
3.3
βH9C3C2 (13) + βH11C6C1
(11)
14.1
2639.2
96
97
98
1479
1491
1536
1473
1489
1530
1470
1499
1552
69.3
6.2
73.4
2.7
6.4
7.4
3.6
βH22C19C21 (12)
νN12N13 (53)
νC14C16 (29)
6673.9
157
9.1
12.1
11.3
νC1C6 (22) + νC1C2 (14) +
νC4C5 (13) + νC3C4 (16)
99
1576
1585
1601
1576
1592
1603
1574
1589
1596
2.2
7.5
6.1
5.9
6.7
9.5
νC2C3 (21) + νC5C6 (19) +
νC4C5 (13)
100
101
15.8
235.7
9.5
νC16C19 (13) + νC14C15
(26) + νC15C17 (14)
65.2
17.6
558.4
1183
10.7
102
103
104
105
1615
1699
1767
2265
1610
1670
1763
2265
1630
1688
1780
2277
7.3
8
12.2
14.5
23.9
41.4
νN33C31 (72)
νO37C36 (83)
νO25C24 (85)
νN42C41 (91)
780.5 126.4
707.2 6.7
11.9
12.6
8.6
61.4
νC27H28 (18) + νC27H29
(52) + νC27H30 (31)
106
107
108
109
110
111
2820
2826
2880
2926
2831
2940
2968
3023
2966
2972
2983
3023
3048
3073
36.1
147.9
1
5.7
6
νC31H32 (25) + νC38H39
(19) + νC38H40 (56)
10.3
18.1
1.4
46
1.1
1.1
1.1
1.1
1.1
νC31H32 (74) + νC38H39
(11) + νC38H40 (14)
84.1
67.8
55
6.1
6.4
6.5
6.5
νC38H39 (70) + νC38H40
(29)
νC27H29 (43) + νC27H30
(54)
15.1
1.3
νC1H7 (41) + νC2H8 (40) +
νC6H11 (16)
40
νC2H8 (40) + νC5H10 (11)
+ νC6H11 (45)
112
113
114
3082
3085
3086
9.1
2.7
3.5
166
1.1
1.1
1.1
6.6
6.6
6.7
2874
2987
24.9
30.1
νC15H18 (99)
νC27H28 (80) + νC27H30
(15)
νC1H7 (46) + νC2H8 (14) +
νC5H10 (32)
115
116
117
118
3061
3086
3092
3099
3101
3116
19.8
2.9
247.8
126
1.1
1.1
1.1
1.1
6.6
6.6
6.7
6.7
3080
3112
νC19H22 (92)
νC1H7 (10) + νC5H10 (55)
+ νC6H11 (32)
17.6
4.4
264.1
51.6
3110
νC3H9 (95)

ACCEPTED MANUSCRIPT
119
120
3200
3431
3201
3465
3121
3469
3.1
72.1
208
1.1
1.1
6.7
8.2
νN34H35 (92)
νN34H35 (100)
68.3
Freq. – frequency, const. –constant, ν – Stretching, β – In-plane bending, τ – Torsional vibration, Γ – Out of plane bending
Table 3
Comparison of 1H and 13C chemical shift (ppm) values of CHPMC.
Atom
H7
HF
B3LYP
8.349
8.235
8.823
8.863
8.378
8.866
9.011
7.999
3.984
4.094
4.231
9.052
8.617
3.851
4.401
Expt.
7.581
7.549
7.933
7.958
7.552
8.406
7.987
7.404
3.957
3.957
3.957
8.257
7.738
4.033
4.037
Atom
C1
HF
B3LYP
132.76
128.78
114.12
151.57
134.08
129.35
150.13
138.84
118.29
127.98
125.47
151.86
150.57
62.314
156.4
Expt.
8.876
8.766
9.336
9.375
8.904
9.378
9.518
8.537
4.642
4.749
4.881
9.136
9.558
4.513
5.047
137.64
133.51
118.26
157.21
139.02
134.09
155.71
143.96
122.6
131.17
122.50
128.76
151.70
128.76
122.50
150.29
139.50
126.38
122.38
123.37
149.75
152.79
55.51
H8
C2
H9
C3
H10
H11
H18
H20
H22
H28
H29
H30
H32
H35
H39
H40
C4
C5
C6
C14
C15
C16
C17
C19
C21
C24
C27
C31
C36
C38
C41
132.67
130.06
157.51
156.16
64.382
162.23
163.56
34.106
116.07
123.0
157.68
33.202
112.02
163.99
23.91
114.35
Expt.-Experimental

ACCEPTED MANUSCRIPT
Table 4
The experimental and computated UV-Visible results of CHPMC in different solvents.
Experimental
TD-DFT/6-31+g(d,p)
Solvent
λ (nm)
347
Absorbance
λ (nm)
347
368
480
350
368
476
349
368
477
349
367
476
Oscillator strength
Assignments
0.364
0.257
f=0.2544
f=0.7742
f=0.0000
f=0.2638
f=0.7560
f=0.0000
f=0.2734
f=0.7451
f=0.0000
f=0.2870
f=0.7144
f=0.0000
H-2 → L (n– σ*)
Benzene
372
H
→ L (n– σ*)
H-1 → L (n– σ*)
H-2 → L (n– σ*)
348
0.611
0.426
Chloroform
DCM
370.5
H
→ L (n– σ*)
H-1 → L (n– σ*)
H-2 → L (n– σ*)
345
370
0.507
0.324
H
→ L (n– σ*)
H-1 → L (n– σ*)
H-2 → L (n– σ*)
344.5
368
0.646
0.434
Ethanol
H
→ L (n– σ*)
H-1 → L (n– σ*)
Table 5
Different property values derived from HOMO-LUMO orbital energies.
Properties
Ip (eV) EA (eV)
8.186 5.8317
∆E (eV)
η (eV)
Χ (eV)
σ (eV-1)
µD
ω (eV2)
0.1145
CHPMC
2.3548
1.1774
7.009
0.8494
6.054

ACCEPTED MANUSCRIPT
Table 6
Mulliken atomic charges of atoms.
Atom HF
B3LYP Atom HF
B3LYP
0.1841 0.1493
-0.551 -0.332
0.8548 0.5767
C1
-0.0973 -0.0124 H22
-0.3218 -0.2922 O23
0.2971 0.5239 C24
-1.0057 -0.9201 O25
0.5172 0.2095 O26
-0.2812 -0.1994 C27
0.1735 0.1304 H28
0.1751 0.1323 H29
0.1942 0.1456 H30
C2
C3
C4
-0.53
-0.444
C5
-0.388 -0.251
-0.068 -0.151
0.1486 0.1728
0.1497 0.1557
0.1507 0.1626
0.2036 -0.269
0.1505 0.1045
0.1765 -0.094
-0.519 -0.225
C6
H7
H8
H9
H10
H11
N12
N13
C14
C15
C16
C17
H18
C19
H20
C21
0.1754 0.134
C31
0.1739 0.1325 H32
0.0678 0.0389 N33
-0.0235 -0.0271 N34
-0.714
-1.1434 H35
0.342
0.3437
0.2197 -0.6621 C36
0.4874 0.8146 O37
0.9776 0.7762 C38
0.2072 0.1286 H39
-0.0494 -0.0909 H40
0.3532 0.2316
-0.524 -0.391
0.0405 -0.009
0.223
0.2297
0.2085 0.1997
0.1352 0.1663
-0.403 -0.42
0.2054 0.157
C41
-1.716 0.1188 N42

ACCEPTED MANUSCRIPT
Scheme 1

ACCEPTED MANUSCRIPT
Fig. 1

ACCEPTED MANUSCRIPT
Fig. 2