Study of molecular structure, chemical reactivity and first hyperpolarizability of a newly synthesized N-(4-oxo-2-phenylquinazolin-3(4H)-yl)-1H-indole-2-carboxamide using spectral?analysis

Article abstract of DOI:10.1016/j.molstruc.2017.05.095

A series of novel Quinazolinone derivatives were synthesized and characterized by various spectroscopic techniques. The nature of reactants and products of chemical reactions has been determined using thermodynamic parameters (H, G, S). The TD–DFT calculation of the compound shows that electronic excitations is n→π^? in nature and compounds having intramolecular hydrogen bonding is obvious in ¹H NMR, ¹³C NMR, FT–IR measurements and ESP map. In ¹H NMR signal of the indolic NH protons appears at 7.26 ppm shows that intramolecular hydrogen is present in compounds. The vibrational analysis designates the presence of intramolecular hydrogen bonding N12–H34?O21 shows in lowering of NH and CO stretching vibrations frequency. The local reactivity descriptors Fukui functions (f_k⁺, f_k^–), local softness's (s_k⁺, s_k^–) and electrophilicity indices (ω_k⁺, ω_k^–) determine the reactive sites within molecule. The computed first hyperpolarizability (β₀) found to be 10.2254×10^?30esu indicating that the compound is non–linear optical (NLO) material.

Full text of DOI:10.1016/j.molstruc.2017.05.095

Accepted Manuscript
Study of molecular structure, chemical reactivity and first hyperpolarizability of a
newly synthesized N-(4-oxo-2-phenylquinazolin-3(4H)-yl)-1H-indole-2-carboxamide
using spectral analysis
Aniruddh Prasad Chaudhary, Shailendra Kumar Bharti, Santosh Kumar, Kumar Ved,
Kant Padam
PII:
S0022-2860(17)30706-8
10.1016/j.molstruc.2017.05.095
MOLSTR 23836
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 17 February 2017
Revised Date: 28 April 2017
Accepted Date: 19 May 2017
Please cite this article as: A.P. Chaudhary, S.K. Bharti, S. Kumar, K. Ved, K. Padam, Study of
molecular structure, chemical reactivity and first hyperpolarizability of a newly synthesized N-(4-oxo-2-
phenylquinazolin-3(4H)-yl)-1H-indole-2-carboxamide using spectral analysis, Journal of Molecular
Structure (2017), doi: 10.1016/j.molstruc.2017.05.095.
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ACCEPTED MANUSCRIPT
GRAPHICAL ABSTRACT
[1]

ACCEPTED MANUSCRIPT
Study of molecular structure, chemical reactivity and first
hyperpolarizability of a newly synthesized N-(4-oxo-2-phenylquinazolin-
3
(4H)-yl)-1H-indole-2-carboxamide using spectral analysis
Aniruddh Prasad Chaudhary, Shailendra Kumar Bharti, Santosh Kumar, Ved kumar, Padam Kant*
Department of chemistry University of Lucknow, Lucknow Uttar Pradesh-226007
E-mail: Kant_padam@lkouniv.ac.in, E-mail:anirudhraj0002@gmail.com
Abstract
A series of novel Quinazolinone derivatives were synthesized and characterized by various
spectroscopic techniques. The nature of reactants and products of chemical reactions has been
determined using thermodynamic parameters (H, G, S).The TD–DFT calculation of the compound
*
shows that electronic excitations is n→π in nature and compounds having intramolecular hydrogen
1
13
1
bonding is obvious in H NMR, C NMR, FT–IR measurements and ESP map. In H NMR signal of
the indolic NH protons appears at 7.26 ppm shows that intramolecular hydrogen is present in
compounds. The vibrational analysis designates the presence of intramolecular hydrogen bonding
N12–H34···O21 shows in lowering of NH and CO stretching vibrations frequency. The local
+
–
+
–
reactivity descriptors Fukui functions (f , f ), local softness’s (s , s ) and electrophilicity indices
k
k
k
k
+
–
(
ω , ω ) determine the reactive sites within molecule. The computed first hyperpolarizability (β )
k k 0
found to be 10.2254 ×ꢀ10ꢁꢂꢃꢄꢅꢆ indicating that the compound is non–linear optical (NLO) material.
Keywords
:
Quinazolinone, MESP, NLO analysis, chemical reactivity, first hyperpolarizability
Introduction
One of the major problems facing humanity today in the context of life threatening disease such as
microbial infections, protozoan Leishmaniasis [1], HIV/AIDS Co infections [2], Quinazoline
derivatives, one of the most active classes of compounds possessing a wide spectrum of biological
properties, for example, antitumor[3-5], anti-inflammatory[6,7], anticonvulsant [8] ,antioxidants [9],
analgesic [10,11] for this reason, total synthesis of natural occurring quinazolinones e.g. Vasicinones
[
12,13] Fumiquinazolinones, Luotonins[14] Circumdatin[15] and Asperlicin[16] have earlier been
reported. Quinazolinone have ability to reduce the C=O and C=N group by transfer of hydrogenation
and have strong coordinating complex towards different metal ions Rh, Pt, Ir, Pd, Os and Ru [17].
Thus we synthesized compounds that related to the natural occurring quinazolinones and
screened them for their Antimicrobial [18,19] and Antileishmanial [20] activity, the compounds were
found promising results with a number 3-aminoquinazolinones with a known structures against
microorganisms, therefore, we aim at this work is to be synthesis of some novel quinazolinone
derivatives and to search for their antimicrobial potentialities. On methylation of 2- carboxylic indole
of compound 1 by the reaction of methanol and sulphuric acid was used as a acid catalyst to form
Methyl-2-indole carboxylate of compound A, further was reacted with hydrazine hydrate with
ethanol, furnished 2-carbohydrazide indole of compound 2. The compound 1 was reacted with
0
compound 2 ethanol used as solvent and heated at 75 C for 3-6 hours to afford the targeted
[2]

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compounds 3. A series of Quinazoline derivatives were screened for their antimicrobial,
antileishmanial activity and characterized by spectroscopic techniques.
In observation of above applications of quinazolinone containing of compound 3 has synthesized and
1
characterized by H NMR, UV–Visible, FT-IR and Mass spectroscopic techniques. The geometry of
compound 3 was optimized and harmonic vibrational frequencies were calculated by DFT/B3LYP
1
level and using 6-31 G(d, p) basis set. The H-NMR chemical shifts were calculated by GIAO method
using same basis set. The results obtained theoretically compared with the experimental observations.
1
The H-NMR chemical shifts and vibrational analysis showed the existence of intramolecular H-
bonding. It is also predicts the transition between HOMO-LUMO in compound 5 by using TD-DFT
approach. Quantum chemical calculations are responsible for the determination of thermodynamic
parameters such as enthalpy (H), entropy (S) and Gibb’s free energy (G) and also predict feasibility of
reactions. Molecular Electrostatic Potential surface (MEPS) investigation along with calculation of
first hyperpolarizability (β evaluates the NLO properties of the compound. The global reactivity
0
)
descriptors and local reactivity descriptor like Fukui functions have been calculated to elaborate
various characteristic properties of the compound 3.
Experimental Protocol:
All the reactions were monitored by thin layer chromatography over silica gel-G and basic alumina
coated TLC plates and TLC was also performed using silica gel 60 F254 plates. The spot on TLC
plates were developed by iodine vapours. The melting points were recorded on an electrically heated
melting point apparatus and are uncorrected. IR spectra were recorded on Beckman Aculab-10, Perkin
Elmer 881 and FT IR 8210 PC, Shimadzu spectrophotometers either on KBr discs or in neat and
-1
values are expressed in cm . Nuclear Magnetic Resonance (NMR) spectra were recorded on either
Bruker Advance DRX-300 MHz or Bruker DRX 200 FT spectrometers using TMS (0.0ppm) as an
internal reference. Chemical shifts (δ in ppm) were reported relative to solvent peak (CHCl in CDCl3
3
at 7.23 ppm and DMSO in DMSO-d at 2.49 ppm) or TMS. Signals were designated as follows: s,
6
singlet; bs, broad singlet; d, doublet; dd, double doublet; t, triplet; m, multiplet and q, quartet. FAB
mass spectra were recorded on JEOL SX 102/DA 6000 mass spectrometer using Argon/Xenon (6 KV,
1
0mA) as the FAB gas. EI mass spectra were recorded on JEOL JMS-D-300 spectrometer with
ionization potential of 70 eV and ES mass on Quantro-II, micro mass.
[3]

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Synthesis of Indole-2-methyl carboxylate (A)
On methylation of indole -2-carboxylic acid with methanol and sulphuric acid was added as acid
catalyst. The reaction mixture was stirred at room temperature for 8-10hrs. After completion of
reaction (Monitored by TLC), the solvent was evaporated on water bath the crud product obtained. It
was purified by a column chromatography in a mixture of hexane and ethyl acetate (3:1). The solid
crystalline compound obtained in good yield 65%.
Synthesis of Indole-2-carbohydrazide (2)
A mixture of methyl indole-2-carboxylate A (0.01 mole) and hydrazine hydrate (.01mole) in absolute
ethanol, (30ml) was heated under reflux 5-7 hrs. After completion of reaction (Monitored by TLC)
The reaction mixture was cooled at room temperature, precipitated solid was recrystallized in absolute
ethanol. The crystalline compound Indole-2-carbohydrazide (2) was obtained in good yield (68%)
Synthesis
of
N-(4-oxo-2-phenylquinazolin-3(4H)-yl)-1H-indole-2-
carboxamide (compounds 3):
2
-Phenyl-3,1-benzoxazin-4-(4H)-one (1) (0.5mole) was treated with Indole-2-carbohydrazide (2)
equimolar proportion of (0.5 mol) using ethanol (25 ml) as a solvent the resulting the reaction mixture
was refluxed for -4- 6 hrs., after completion of the reaction was (Monitoring by TLC), the excess of
solvent was distilled off on rota vapour and the resulting solid obtained was dried and recrystallized
by rectified sprit, affording the corresponding compounds (3) as colourless crystalline solid in good
yields(70%).
IR (KBr Solid), 3399 NH, 3021 (CH), 1959 (C=0), 1616 (C=C), 1403 (C=N), 1316 (C=C), 1059 (C-O
1
enol group); H NMR (300MHz, CDCl ): δ 7.26 (2NH, bs), 7.53-7.60 (m, 5H), 7.48 (s, 1H), 7.69 (d,
3
J= 8.01 Hz, 2H), 7.80 (t, J = 9.00Hz, 2H), 7.83 ( t, J = 7.1 Hz, 2H), 8.23 (d, J = 7.8 Hz, 2H), 8.3 (dd, J
1
3
=
7.2Hz, 2H), C NMR (300 MHz, CDCl ): δ 117.20, 127.42 x 2, 128.46 x 3, 128.51 x 3, 128.74 x 3,
3
+
1
28.94 x 3, 130.41 x 2, 132.82 x 2, 136.77 x 3, 147.1 x 3, 157.3, 159.87: ESMS: m/z 381.2 [M + 1]
33.96, 224.11
3
Results and discussion:
Thermochemistry
On theoretical study of the reactants 2-Phenyl-3,1-benzoxazin-4-(4H)-one (1), Indole-2-
carbohydrazide (2) and ethanol used as a solvent. The reaction mixture was reflux and
monitoring the reaction mixture through thin layer chromatography. After completion of
reaction, solvent was removed in vaccuo, to furnished the final product, N-(4-oxo-2-
phenylquinazolin-3(4H)-yl)-1H-indole-2-carboxamide (3) in Scheme 1 The value of Enthalpy
(H/a.u.), Gibbs free energy (G/ a.u.) and Entropy [S(cal/mol/K)] of (3), (4), (5),(a) are
obtained with help of Gaussian 09 program. These calculated thermodynamic parameter and
[4]

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0
their change for Reaction, at 25 C are listed in Table 1. The positive values of enthalpy
change (∆H) and negative value of entropy shown that reaction is favourable however;
positive value of Gibbs free energy (∆G) change indicates that reaction is unfavourable . That
0
is why the reaction is non-spontaneous. At 25 C, thermodynamic equilibrium constant (K )
T
for this reaction is calculated as 0.99489. The value of Keq < 1 indicates that the reaction will
require elevation of temperature and presence of catalyst.
UV–visible spectra
To gain insight into the nature of electronic transitions occurring in the experimental UV-visible
spectrum of compound 3 time-dependent DFT (TD-DFT) calculations were performed gaseous phase
as well as using the solvent parameters matching with chloroform. The basis set used for calculations
was 6-31G (d,p) and the functionals were B3LYP and Cam-B3LYP. Also cLR (corrected linear
response) calculations were performed using Cam-B3LYP/6-31G(d,p) parameters. The experimental
and calculated UV–Vis spectra in region 250-400 nm are shown in Fig 5. The experimentally as well
as theoretically calculated vertical excitation energies, wavelengths, oscillator strengths and orbital
transition are itemized in Table 4. In present work, the theoretical calculation shows one more intense
electronic transition at ꢇꢈꢉꢊ= 292.86/298.13nm in gas/chloroform solvent with an oscillator strengths
f = 4.2738/4.3050 and it has good agreement with the observed experimental data at ꢇꢈꢉꢊ.= 297 nm
in chloroform. It is further confirmed by the calculation of absorption maximum with the help of cLR
methods which shows more intense electronic transition at ꢇꢈꢉꢊ = 297.53/277.13 nm in
gas/chloroform solvent with an oscillator strengths f = 4.6806/4.6765 and it has good agreement with
the above observed experimental data. The difference between experimental and theoretical results
∗
may be due to solvent effects. Due to this effect ꢋ → ꢋ in polar solvent shows bathochromic shift
∗
(
red shift) however n →ꢀꢋ shows hypsochromic shift (blue shift). In view of the theoretically
calculated absorption spectra, the wavelength for the maximum absorption (ꢋ → ꢋ∗ electronic
transition), results from the highest occupied molecular orbital (H-1, 98) to the second excited
unoccupied molecular orbital (L+2, 102) in the chloroform. Fig.8 of Supplementary material shows
that the orbitals H, H-1 and H-6 are localized over C23−C24 of Indole ring, C14−C15 of benzene
ring and C10−O11 of carbonyl group of benzaoxinone ring however orbitals L and L+2 are localized
over C10−O11 of carbonyl group in benzaoxinone ring and N7−C8 bonds of benzaoxinone ring
respectively. According to molecular orbital theory the nature of these electronic transitions are
∗
∗
assigned to be ꢋ(C23−C24)→ ꢋ (C10−O11), ꢀꢋ(C14−C15)→ꢀꢋ (C10−O11), n(C10−O11)→
∗
∗
ꢀ
ꢋ (C10−O11)and ꢋ(C14−C15)→ꢀꢋ (N7−C8) respectively.
[5]

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Vibrational analysis and theoretical prediction of spectra of the compounds
The vibrational analysis of N-(4-oxo-2-phenylquinazolin-3(4H)-yl)-1H-indole-2-carboxamide 3 has
been found 45 atoms, belong to C point group and possess 129 normal modes of vibration. The
1
vibrational spectral assignments have been performed based on the recorded FT-IR spectra and
theoretically analysis. The harmonic vibrational frequencies are calculated for the compound 3 by
DFT/B3LYP level with 6-31G(d,p) basis of theory. The experimental, calculated frequencies and
potential energy distribution (PED) of the target compound are summarized in Table 5.
N–H vibrations
The compound 5 possesses two NH vibrations first NH in indole ring and second is hydrazide NH
-1
vibrations. The asymmetric stretching of indolic NH calculated at 3528 cm whereas observed at
-1
-1
3
400 cm and reported at 3402 cm in the IR absorption spectra [11 ] and hydrazide NH stretching
-1
vibration calculated at 3465 cm and observed stretching vibration merged in indolic NH due to
exchangeable with deuterated chloroform.
C–H vibration
-1
In general most of the hetero aromatic compounds has showed IR frequency at 3085 cm due to
-1
asymmetric C-H stretching.[ 12] The compound (5) have observed bands at 3036 cm whereas as
-1
calculated bands at 3148 cm in FT-IR are assigned to C-H stretching vibrations As viewed by the
PED, these modes involve approximately 92% contribution suggesting that they are stretching modes.
C-C vibrations
The C–C IR vibrations were found theoretically in the various ranges at 1021, 1083, 1301, 1315,
-
1
1
463, 1575, 1596 and1604 cm .as similar to the reported values at 1043,1303,1443, 1470, 1533 and
-1
-
1
601cm [13] however observed value of C-C stretching vibrations are 1312 and 1571 cm
1
respectively in FT-IR. Since the synthesized compound 5 was confirmed both theoretically and
reported values.
C=O vibrations
The investigated compound 5 contain two carbonyl groups (C10=O11, C19=O21) due to asymmetric
nature of molecule. The stretching vibration of both carbonyl carbons is observed at 1765 and 1610
-
1
-1
cm whereas this is calculated at 1631 & 1620 cm in theoretical IR spectrum. The C=O stretching
-1
vibrations are reported at 1703 cm [14 ]
[6]

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1
13
H NMR and C NMR spectroscopy
2
-Phenyl-3, 1-benzoxazin-4-(4H)-one 3 and Indole-2-carbohydrazide 4 product were
obtained depending on the amount of equimolar proportion of ethanol using as a solvent and reaction
1
13
conditions. The experimental and calculated H, C NMR and chemical shifts (ꢌ ppm) of N-(4-oxo-2-
phenylquinazolin-3(4H)-yl)-1H-indole-2-carboxamide 3 are given in Table 2 & 3 and experimental
spectrum is shown in Supplementary data Figs. 2 and 3 respectively. The chemical shifts have been
calculated by using DFT (B3LYP) methods with 6-31G (d,p) basis set, employing GIAO approach.
1
The experimental H NMR spectrum of N-(4-oxo-2-phenylquinazolin-3(4H)-yl)-1H-indole-2-
carboxamide 5 shows the presence of singlet at s 7.26 ppm for amide NH protons while the calculated
value obtained at 9.13 ppm while other Indolic proton (NH) appears at 7.26 ppm as comparable to the
1
3
calculated value at 8.65 ppm. The experimental C NMR spectrum shows two carbonyl carbon
(
C=O) signals one appears at 159.87 ppm, present in benzaoxinone ring others at 157.3 ppm that
1
13
shows amide linkage. Instead of H and C NMR chemical shifts, mass spectrum also shown in
+
supplementary data Fig 4. we also confirm the molecular ion peaks mass spectrometer [M+1] ,
corresponds to molecular formula C H N O .
2
3
16
4
2
NLO properties
The development of materials with large nonlinear optical (NLO) properties has great interest
in the past few times. These materials find several device applications such as optical switches and
electronics device [15-16]. These are very important in areas such as telecommunications, optical
interconnections and signal processing [17-18.].The first order hyperpolarizability (ꢍ ), electric
ꢃ
dipole moment (µ) and polarizability (α) are calculated using B3LYP/6-31G(d,p) basis set from
Gaussian 09W . The calculation of magnitude of total static dipole moment (μꢎꢏꢎ), isotropic
polarizability (ꢐ ), anisotropy of the polarizability,ꢀ∆ꢐꢀand first hyperpolarizability(ꢍ ) from
ꢃ
ꢃ
complete equations as given below.
ꢑ
ꢑ
ꢑ ꢑ
μ =ꢀ(μ + μ + μ )
ꢊ
ꢒ
ꢓ
ꢔꢕꢕꢖꢔꢗꢗꢖꢔꢘꢘ
ꢂ
ꢀꢀꢀꢐꢃ=
ꢑ
ꢑ
ꢑ
α = 2ꢁꢙ⁄ꢑ ꢚꢛꢐꢊꢊ − ꢐ ꢜ + ꢛꢐ − ꢐ ꢜ + (ꢐ − ꢐ ) ꢝ
ꢑ
ꢒꢒ
ꢒꢒ
ꢓꢓ
ꢓꢓ
ꢊꢊ
ꢑ
ꢑ
ꢑ
ꢑ
ꢍ =ꢀꢛꢍ + ꢍ + ꢍ ꢜ
ꢃ
ꢊ
ꢒ
ꢓ
And
ꢍꢊ =ꢀꢍ
ꢊꢊꢊ
+ ꢍꢊꢒꢒ + ꢍꢊꢓꢓ
+ ꢍꢊꢊꢒ + ꢍꢒꢓꢓ
+ ꢍꢊꢊꢓ + ꢍꢒꢒꢓ
ꢍꢒ =ꢀꢍ
ꢒꢒꢒ
ꢍꢓ =ꢀꢍ
ꢓꢓꢓ
[7]

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The total molecular dipole moment and mean first hyperpolarizability is 2.2629 Debye
andꢀ10.2254 ×ꢀ10ꢁꢂꢃꢄꢅꢆ respectively, as shown in Tables 7. Total dipole moment of molecule is
approximately two times greater than that of urea and first hyperpolarizability of compound 3 is
twenty seven times greater than that of urea (µ and β of urea are 1.3732 Debye and 0.3728ꢀ ×
ꢀ
10ꢁꢂꢃꢄꢅꢆ, 6-31G (d,p) respectively [18-21]. Considering the molecule used in the comparative
purposes of the NLO properties of molecular systems. Thus, the studied compound can be regarded as
a good applicant for NLO material
Chemical reactivity
The chemical reactivity of molecule is described in three ways as Global and local electronic
descriptors.
1
.1 Global reactivity descriptors
The chemical reactivity and site selectivity of the molecular systems have been determined on
the basis of Koopman’s theorem [22-23]. Global reactivity descriptors as electro negativity (χ)= –
1
/2(εLUMO + εHOMO), chemical potential (ꢀ) = 1/2 (εLUMO + εHOMO), global hardness (η) = 1/2 (εLUMO –
2
εHOMO), global softness (S) = 1/2η and electrophilicity index (ω) = ꢀ /2η are highly successful in
predicting global reactivity trends [24-25]. According to Parr et al. [26], electrophilicity index (ω) is a
global reactivity index similar to the chemical hardness and chemical potential. This is positive and
negative definite quantity. This new reactivity index measures the stabilization in energy when the
system acquires an additional electronic charge (∆N) from the environment. The direction of the
charge transfer is completely determined by the electronic chemical potential of the molecule because
an electrophile is a chemical species capable of accepting electrons from the environments and its
energy must decrease upon accepting electronic charge. Therefore, its electronic chemical potential
must be negative. The energies of frontier molecular orbital’s (εHOMO, εLUMO), energy gap (εLUMO
HOMO), electronegativity (χ), chemical potential (ꢀ), global hardness (η), global softness (S), global
electrophilicity index (ω) for (1), (2), (3) and ECT for reactant system [(1)↔(2)] are listed in Table
0. The global elecrophilicity index (ω = 3.357 eV) for (3) shows that it behaves as a strong
electrophile.
–
ε
1
Electrophilic charge transfer (ECT) = (∆Nmax)A–(∆N ) is defined as the difference between
max B
the ∆Nmax= -ꢀ/η values of interacting molecules. If we consider two molecules (1) and (2) approach to
each other (i) if ECT > 0, charge flow from (2) to (1) (ii) if ECT < 0, charge flow from (1) to (2) [27-
2
8]. ECT is calculated as 0.3773 i.e ECT > 0 for reactant system [(1)↔(2)], which indicates that
charge flows from (2) to (1). Therefore, (1) acts as electron acceptor (electrophile) and (2) is electron
donor (nucleophile). The high value of elecrophilicity index and low value of chemical potential for
(
1) also favours its electrophilic behaviour. In same way, the low value of electrophilicity index and
high value of chemical potential for (2) also favours its nucleophilic nature.
[8]

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Molecular electrostatic potential
The molecular electrostatic potential (MESP) is related to the electronic density and is a very useful
descriptor for determining sites for electrophilic as well as nucleophilic attack and hydrogen–bonding
interactions [29-31]. These are also provides a visual method to understand the relative polarity of a
molecule and molecular electrostatic potential counter map are made by B3LYP/6-31G(d,p) method
using Gauss view 9.0 program. The molecular electrostatic potential contour surface of compound 3 is
shown in the Fig 6.The different values of the electrostatic potential at the surface are represented by
different colours. Potential increases in the order red < yellow < green < light blue < blue [32-34]. The
colour scheme for the MESP surface is red-electron rich (partially negative charge) and related to
electrophilic reactivity, yellow- slightly electron rich region; green-neutral; light blue-slightly electron
deficient region and blue-electron deficient( partially positive charge) and related to nucleophilic
reactivity respectively [35,36]. The MEP map represents that the region of maximum negative
electrostatic potential is situated around C10 & O11 with MEP value around -5.632 a.u however the
most positive region is found on N9 & N12 with a value of +5.632a.u. So, it is expected that the most
preferred region for electrophilic and nucleophilic attack is around C10 & O11 and N9 & N12,
respectively. The MEP maps give suitable information for that region where the compound can make
hydrogen–bonding interactions
.
Conclusions:
For the title compound 3 we have calculated vibrational frequencies, UV-Visible, MESP surfaces,
1
13
NLO properties, H –NMR and C-NMR chemical shifts theoretically as well as experimentally. We
1
13
found that all theoretical results have good agreement with experimental data. The H –NMR and C-
NMR calculated by GIAO method showed good accuracy with experimental signal. We also found
that title compound 3 have great biological and pharmacological significance such as antimicrobial,
antileishmanial etc. the title of compound 3 is also characterized by mass spectrophotometry.
Acknowledgement:
Aniruddh Prasad chaudhary is thankful to University grant commission (UGC), New Delhi, India for
providing financial support. We are also thankful to Department of chemistry University of Lucknow
for providing Central facility for computational research
.
[9]

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Chemistry 126 (2011) 1033–1038
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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 101 (2013) 91–99
2. M. Arivazhagan , J. Senthil kumar, Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy 137 (2015) 490–502
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2
2
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3. N. Prabavathi, N. Senthil Nayaki, Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy 129 (2014) 572–583
4. N. Prabavathi, N. Senthil Nayaki, Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy 129 (2014) 572–583
5. S. M. Soliman , M.Hagar, F. Ibid, E. Sayed, H. E. Ashry, Spectrochimica Acta Part A:
Molecular and Biomolecular Spectroscopy 145 (2015) 270–279
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6. A. Sethi, R. Prakash, Journal of Molecular Structure 1083 (2015) 72–81
7. A. Barhoumi, T. Mhiri, T. Dammak J. J. Suñol, M. Belhouchet, Journal of Molecular
Structure1128 (2017) 544–551
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8. S. M. Soliman , M.Hagar, F. Ibid, E. Sayed, H. E. Ashry, Spectrochimica Acta Part A:
Molecular and Biomolecular Spectroscopy 145 (2015) 270–279
9. N. Prabavathi, N. Senthil Nayaki, Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy 129 (2014) 572–583
0. M.V.S. Prasad, K. Chaitanya, N. UdayaSri, V. Veeraiah, Journal of Molecular Structure
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047 (2013) 216–228
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33. R.N. Singh , A.Kumar, R.K. Tiwari, P. Rawat, Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy 113 (2013) 378–385
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of Molecular Structure 1107 (2016) 137-144
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242
1. P. Govindasamy , S. Gunasekaran,
Issaoui,
H.
Ghalla,
S.
Muthu,
H.T.
Flakus,
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Biomolecular Spectroscopy 136 ( 2015) 1543–1556
2. B. Sylajaa,, S. Gunasekaranb, S. Srinivasan Optik 127 (2016) 5055–5064
[11]

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Molecular Structure 1089 (2015) 222–232
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Molecular and Biomolecular Spectroscopy Volume 138, 5 March 2015, Pages 900–912
[12]

ACCEPTED MANUSCRIPT
Scheme: The scheme showed synthetic pathway of N-(4-oxo-2 phenylquinazolin-3(4H)-yl)-1H-
indole-2-carboxamide 3 Where (1) & (2) indicates reactants and 3 is product and 4 is side product in
the form of water.
Figure Caption:
Scheme 1 Optimized geometry of reactants (1, 2), product (3) and side product water (4)
Figure 1 Optimized geometry product (3
1
Figure 2 Experimental H NMR spectrum of (3) in CDCl solvent
3
1
3
Figure 3 experimental C NMR spectrum of (3) in CDCl solvent
3
Figure 4 Experimental mass spectrum
Figure 5 Experimental and theoretical UV-Visible spectrum
Figure 6 Comparison between theoretical and experimental IR spectra for (3)
Figure 7 Molecular electrostatic potential (ESP) map of (3)
Figure 8 HOMO-LUMO Transitions
Table caption:
Table 1. Calculated thermodynamic parameters: Enthalpy (H / a.u.), Gibbs free energy (G / a.u.) and
Entropy [S / (cal/mol–K)] of (1), (2), (3), (4) and their change for Reaction, at 25 °C.
1
Table 2. Calculated and experimental H NMR chemical shifts (δ / ppm) of compound in CDCl -
3
solvent at 25 °C.
1
3
Table 3. Calculated and experimental C NMR chemical shifts (δ / ppm) of compound in CDCl -
3
solvent at 25 °C.
Table 4. Calculated and experimental electronic excitations for (3): E / eV, oscillatory strength (f),
(
λmax / nm) at TD–DFT/B3LYP/6–31G(d,p) and Cam-B3LYP/6–31G(d,p) level.
Table 5. Experimental and theoretical [calculated at B3LYP/6–31G(d,p) level] vibrational
–
1
-1
wavenumbers of (3) and their assignments: Wavenumbers ( / cm ), intensity (K mmol ).
Table 6. Calculated Dipole moment (µ ), Polarizability (|α |), anisotropy of Polarizability (ꢀα), First
0
0
Hyperpolarizability (β ) and their components, using B3LYP/6–31G(d,p).
0
Table 7. Calculated εHOMO, εLUMO, energy band gap (ε – ε ), chemical potential (ꢀ), electronegativity
L
H
(
χ), global hardness (η), global softness (S), global electrophilicity index (ω) for (1), (2), (3) and
Elecrophilicity based charge transfer (ECT) for reactant system [(1)↔(2)].
+
+
+
Table 8. Selected electrophilic reactivity descriptors (f , s , ω ) for reactant (1) and nucleophilic
k
k
k
–
–
k
–
reactivity descriptors (f , s , ω ) for reactant (2), using Mulliken atomic charges.
k
k
+
–
+
–
Table 9. Selected reactivity descriptors as Fukui functions (f , f ), local softnesses (s , s ), local
k
k
k
k
+
–
electrophilicity indices (ω , ω ) for (3), using Mulliken atomic charges.
k
k
[13]

ACCEPTED MANUSCRIPT
Table 1. Calculated thermodynamic parameters: Enthalpy (H / a.u.), Gibbs
free energy (G / a.u.) and Entropy [S / (cal/mol–K)] of (1), (2), (3), (4) and their
change for Reaction, at 25 °C.
(
1)
(2)
(3)
(4)
Reaction
0.189
H
G
S
-743.941
-743.994
111.080
-587.491
-587.539
100.183
-1254.848
-1254.925
160.658
-76.394
-76.416
45.116
∆H
∆G
∆S
0.192
-5.489
1
Table 2. Calculated and experimental H NMR chemical shifts (δ / ppm) of
compound in CDCl -solvent at 25 °C.
3
Atom
H30
H31
H32
H33
H34
H35
H36
H37
H38
H39
H40
H41
H42
H43
H44
H45
δcalcd.
7.9704
8.3078
8.1721
8.7778
9.1329
8.5855
7.9118
7.7219
7.7253
8.301
δexp.
Assignment
8.3
dd,2H, (J=7.2 Hz) benzaoxinone ring
8.23
7.26
d, 2H, (J=7.8 Hz) benzaoxinone ring
s ,1H amide NH
7.53-7.60
m, 5H benzene ring
8.6475
7.4253
7.6691
7.7659
7.5753
8.1186
7.26
7.48
7.69
7.80
S ,1H Indole ring NH
S, 1H Indole five member ring
d,1H (J = 8.01 Hz) Indole six member ring
t, 2H(J =9.0 Hz) Indole six member ring
7.69
d, 1H (J = 8.01 Hz) Indole six member ring
[14]

ACCEPTED MANUSCRIPT
1
3
Table 3. Calculated and experimental C NMR chemical shifts (δ / ppm) of
compound in CDCl -solvent at 25 °C.
3
Atom
C1
δcalcd.
δexp.
Assignment
122.6973
131.296
C2
128.94-132.82
Benzaoxinone ring
C3
125.0893
145.1814
119.5752
127.1185
154.9916
C4
132.54-136.77
Benzaoxinone bridged head
C5
C6
128.94-132.82
147.1
Benzaoxinone ring
Benzaoxinone ring between both nitrogen
C =O groups in benzaoxinone ring
benzene ring
C8
C10 162.5676
C13 131.6287
C14 129.7846
C15 124.4582
159.87
130.41
C16
127.853
127.2-128.74
Benzene ring
C17 122.4702
C18 126.1606
C19 159.6925
C20 125.1501
C23 134.9564
C24 125.7714
C25 102.2803
C26 107.9365
C27 122.2289
C28 117.0865
157.3
C =O groups amide linkage
Indole five member ring
128.46
127.42
Indole bridged carbon
128.51
Indole five member ring
1
17.2-127.4
Multiplet indole six member ring
C29
119.464
[15]

ACCEPTED MANUSCRIPT
Table-4 Calculated and experimental electronic excitations for (3): E / eV, oscillatory strength (f), (λmax / nm) at
TD-DFT B3LYP/6–31G(d,p) and Cam-B3LYP/6–31G(d,p) level
B3LYP/6-31G(d,p)
Excitations
9→100 (H→L)
8→100 (H-1→L)
solvent
λmax
λmax
E (eV)
(f)
Assignment
Exp.
calcd.
318.56
326.45
gas
3.8920 0.1040
3.7979
9
9
CHCl3
322
π→π*
0
.1236
gas
308.74
4.0158 0.3606
*
π→π
CHCl3
gas
284
297
308.22
292.86
4.0226 0.2045
4.2738 0.1946
*
9
9
8→102 (H-1→L+2)
3→100 (H-6→L)
π→π
CHCl3
gas
298.13
249.72
4.3050 0.1946
4.9650 0.1534
*
n→π
CHCl3
gas
240
322
284
297
240
252.06
4.9583 0.1347
4.3602 0.5603
4.4151 0.2905
4.6806 0.2383
5.4108 0.1052
Cam-B3LYP/6–
1G(d,p)
99→100 (H→L)
284.35
π→π*
π→π*
π→π*
n→π*
3
98→100 (H-1→L)
2
80.82
iop(10/74=10)
scrf=pisalr
9
9
8→102 (H-1→L+2)
3→100 (H-6→L)
297.53
229.14
td=noneq
Cam-B3LYP/6–
99→100 (H→L)
322
284
297
240
284.50
280.95
277.13
229.21
4.3580 0.5667
4.4130 0.2895
4.6765 0.1091
5.4092 0.2379
π→π*
π→π*
π→π*
n →π*
3
1G(d,p)
98→100 (H-1→L)
iop(10/74=10)
scrf=pisalr
td=noneq
98→102 (H-1→L+2) CHCl3
93→100 (H-6→L)
[16]

ACCEPTED MANUSCRIPT
Table 5. Experimental and theoretical [calculated at B3LYP/6–31G(d,p) level] vibrational wavenumbers
–
1
-1
of (3) and their assignments: Wavenumbers ( / cm ), intensity (K mmol ).
Exp. Assignment (PED) ≥ 5 %
unscal.
scaled Exp.
3119 3400
3114
IRin
3
3
246
241
0.18
ν(N22H40)(98)
19.29 ν(C3H32)(40)ν(C6H33)(14)-(δas-R1)(13)-ν(C16C17)(12) ν(C2H31)(8)
ν(C1H30)(7)
3
3
1
1
1
216
208
698
687
670
3090 3036 30.97 ν(C26H42)(42)-ν(C29H45)(27)-ν(C28H44)(22)ν(C27H43)(8)
3082 2926 14.06 ν(C15H36)(47)-ν(C17H38)(45)ν(C18H39)(4)
1631 1765
57.9
ν(C10O11)(43)ν(C19O21)(15)-ν(C5C10)(9)(δtrigonal-R2)(5)
1620 1610 441.22 ν(C19O21)(39)-ν(C10O11)(13)-ν(C19C20)(9)-δ(N12H34)(7)
1604
1596
74.61 ν(C1C6)(16)-ν(C2C3)(13) ν(C3C4)(13)-ν(C5C6)(10)-(δas-R1)(7)
δ(C1C6H33)(6)ν(C5C10)(5)-δ(C3C4H32)(5)
-
1
661
640
5.81
ν(C14C15)(20)ν(C17C18)(19)(δas- R3)(9)-ν(C13C14)(6)-
δ(C14C15H35)(6) δ(C13C18H39)(5)-ν(C13C18)(5)-ν(C16C17)(5)
1
1575 1571 24.95 ν(C16C17)(19)-ν(C15C16)(17)-ν(C13C18)(14)ν(C13C14)(12)
δ(C16C17H37)(10)-(δas- R3)(9)
1538 1540 295.16 ν(C7N8)(46)-ν(C8C13)(8)-ν(C4N7)(7)(δas-R2)(5)
-
1
601
585
1
1523
180.87 ν(C20C25)(29)-ν(C19O21)(10)-ν(C19C20)(8)-ν(C23C26)(8) δ(as-R4)(7)
δ(C20C25H41)(6) -δ(C27C28H43)(5)
-
1557
1496
106.72 (ρ– N9N12H34)(15) δ(C14C15H36)(10) δ(C13C18H39)(9)
δ(C17C18H38)(8)-δ(C14C15H35)(6)-δ(N12H34)(5)ν(C15C16)(5)
-ν(C13C14)(5)
1
549
521
1488 1410 132.27 (ρ– N9N12H34)(44)-δ(N12H34)(14)ν(C19N12)(7)
1
1461
117.79 δ(C1C6H33)(20)-δ(C3C4H32)(19) ν(C4C5)(14)-ν(C4N7)(7)
δ(C1C2H30)(5)
-
ν(C2C3)(5)
ν(C27C28)(12)-ν(C20N22)(10)ν(C24C29)(9)-ν(C28C29)(7)ν(C19C20)(7)
ν(C23C24)(6)-δ(as-R4)(6)δ(C28C29H44)(5)ν(C23C26)(5)-ν(C26C27)(5)
1427
1400
1389
1371
1345
1334
23.5
-
42.25 δ(C28C29H44)(12) -δ(C20C25H41)(10) -δ(C23C26H42)(10)-
ν(C24C25)(9) 1ν(C10O11)(7)-ν(C26C27)(6)ν(C20N22)(5)
65.67 ν(C4C5)(15) ν(C1C6)(12) ν(C2C3)(11)-ν(C5C6)(10)-ν(C3C4)(9)-
ν(C1C2)(8) δ(C14C15H35)(8) δ(C13C18H39)(6)
1
383
368
1329
1315
17.44 ν(C8N9)(15)-ν(C8C13)(13)-ν(N9N12)(8) δ(C13C18H39)(7)
12.13 ν(C13C18)(18)-ν(C13C14)(16)ν(C16C17)(11)ν(C14C15)(11)
1
-ν(C15C16)(10)-ν(C17C18)(9)
[17]

ACCEPTED MANUSCRIPT
1
354
289
1301 1312 152.77 ν(C23C24)(15)-ν(C23N22)(12)-ν(C24C25)(12)ν(C28C29)(9)ν(C26C27)(7)
1238 1268 123.77 δ(C20N22H40)(25)δ(C23C26H42)(14)ν(C23C26)(12) -1ν(C10O11)(11)
δ(as-R4)(6)-ν(C24C25)(5)
1
1276
1272
1262
1232
1209
1226 1262 97.48 (δtrigonal-R5)(13)ν(C23N22)(12) -1ν(C10O11)(8) -δ(C20N22H40)(7)
-
ν(C24C25)(7)-ν(C24C29)(6)ν(C19C20)(5)-ν(C19N12)(5)
1222 1252 134.25 ν(C10N9)(10)ν(C7N8)(10) ν(C4N7)(9)-(δtrigonal-R1)(9) δ(C1C6H33)(8)
ν(C8N9)(6)-ν(N9N12)(5)-ν(C5C10)(5)
1213 1207 67.88 δ(C20C25H41)(11)-ν(N9N12)(11)-ν(C3C4)(7)ν(C19N12)(6)ν(C5C10)(6)
δ(C20N22H40)(6)-ν(C24C25)(5)-δ(C3C4H32)(5)(δtrigonal-R5)(5)
81.49 δ(C20C25H41)(23)ν(N9N12)(11)-δ(C1C2H30)(8)δ(C28C29H44)(6)
ν(C19C20)(6) -δ(C27C28H43)(5)
1162 1078 52.01 δ(C27C28H43)(15)δ(C23C26H42)(12) -δ(C28C29H44)(11)
ν(C10O11)(9)δ(C20C25H41)(6) δ(C3C4H32)(5)-δ(C2C3H31)(5)
ν(C24C25)(5)
-
-
1184
-
1
-
1
169
137
1123 1021 22.61 ν(C10N9)(28)-ν(C8N9)(14)-(δtrigonal-R3)(6)
1093 1012 12.28 ν(C20N22)(18)-ν(C19N12)(15)δ(C20C25H41)(15)(δtrigonal-
R1)(5)δ(C20N22H40)(5)
1
9
30
894
818
965
856
28.52 (δtrigonal-R1)(22)-(δtrigonal-R5)(16)(δtrigonal-R2)(9)-δ(as-R4)(7)
33.38 ω(C25H41)(42) δoop(C19C20)(19)(τ–R4)(13) -δip(C19C20)(7)
852
-
(τ–R4)(5)(ω–C27H43)(5)
18.76 (ω–C1H30)(23)-(R1-Puckering)(10)(ω–C2H31)(8)(ω–C6H33)(8)
R2-Puckering)(7)(ω–C3H321)(5) δoop(C8C13)(5)
808
777
(
8
05
77
774
746
765
734
62.74 (R3-Puckering)(22) -δoop(C8C13)(21)(ω–C16H37)(13)(ω–C1H30)(8)
91.68 (ω–C27H43)(20)(ω–C28H44)(19)-(ω–C26H42)(16)δip(C19C20)(16)
7
(
ω– C29H45)(14) -δoop(C19C20)(10)
20.36 (δas-R1)(21) δ(C5C10O11)(14)-(R3-Puckering)(12)-(δas-R1)(7)
ω(N22H40)(81)(τ–R4)(8)
6
79
57
653
632
684
6
606 84.41
Proposed assignment and potential energy distribution (PED) for vibrational modes: Types of vibrations:
ꢞ– stretching, ꢟsc – scissoring, ꢠ – rocking, ꢡ – wagging, ꢟ-deformation, ꢟs – symmetric deformation, ꢟas
–
asymmetric deformation, ꢢ – torsion.
[18]

ACCEPTED MANUSCRIPT
Table 6. Calculated Dipole moment (µ ), Polarizability (|α |), anisotropy of
0
0
Polarizability (ꢀα), First Hyperpolarizability (β ) and their components, using
0
B3LYP/6–31G(d,p).
Dipole moment
0.7712 αxx
Polarizability
Hyperpolarizability
µx
µy
µz
µ
421.274 βxxx
-1078.2
371.327
-191.64
-344.42
113.962
-64.047
17.0475
93.3451
32.2971
-16.282
10.2254
2.127 αyy
-0.0406 αzz
2.2629 αxy
αxz
35.5001 βxxy
266.416 βxyy
-42.771 βyyy
21.3624 βxxz
195.622 βxyz
35.7256 βyyz
119.066 βxzz
βyzz
αyz
α0
ꢀα
βzzz
β0
-24
-30
µ in Debye; |α | and ꢀα in 10 esu; β in 10 esu,
0
0
0
Table 7. Calculated εHOMO, εLUMO, energy band gap (ε – ε ), chemical potential (ꢀ),
L
H
electronegativity (χ), global hardness (η), global softness (S), global electrophilicity index
(
[
ω) for (1), (2), (3) and Elecrophilicity based charge transfer (ECT) for reactant system
(1)↔(2)].
εH
εL
εL– εH
Χ
ꢀ
η
S
(ω)
ECT
(
(
(
1) -6.3413 -1.8825 4.4588
1119
-4.1119 2.2294 1.1147 3.7920
0.3773
2) -5.5832 -1.0569 4.5263 3.3200 -3.3200 2.2631 1.1315 4.5263
3) -5.9710 -1.6488 4.3225 3.8097 -3.8097 2.1612 1.0806 3.3577
–
1
ε , ε , ε – ε , χ, ꢀ, η, ω (in eV) and S (in eV ) 27.2116
H
L
L
H
[19]

+
+
+
Table 8. Selected electrophilic reactivity descriptors (f , s , ω ) for reactant (1) and
ACCEPTED MANU
k
SC
k
RIPT
k
–
k
–
k
–
k
nucleophilic reactivity descriptors (f , s , ω ) for reactant (2), using Mulliken atomic
charges.
sites
+
+
+
–
–
–
fk
sk
ωk
sites
fk
sk
ωk
C2
C3
0.0831
0.0635
0.0926
0.0707
0.0673
0.3151
0.2407
0.2290
0.3693
O17
N18
N20
0.0534
0.0582
0.0756
0.0604
0.0658
0.0855
0.2417
0.2634
0.3421
C6
0.0604
C8
0.0974
0.1115
0
0
.1085
C10
.1262
0.5047
+
k
–
k
+
k
–
k
–1
+
k
–
k
f , f (in e ); s , s (in eV ) and ω , ω (in eV)
+
k
–
k
+
k
Table 9. Selected reactivity descriptors as Fukui functions (f , f ), local softnesses (s ,
–
k
+
k
–
k
s ), local electrophilicity indices (ω , ω ) for (3), using Mulliken atomic charges.
+
+
+
–
–
–
sites
fk
sk
ωk
sites
fk
sk
ωk
C1
C2
0.0699
0.0599
0.0681
0.0662
0.0592
0.0596
0.0755
0.0647
0.0735
0.0715
0.0639
0.2347
0.2011
0.2286
0.2222
0.1987
0.2001
N7
N9
0.0413
0.0063
0.0416
0.0187
0.0237
0.0446
0.0068
0.0449
0.0202
0.0256
0.1386
0.0211
0.1396
0.0627
0.0795
C16
C25
C27
O11
N12
O21
C29
0.0644
+
k
–
k
+
–
k
–1
+
k
–
f , f (in e ); s , s (in eV ) and ω , ω (in eV)
k
k
[20]

ACCEPTED MANUSCRIPT
Figure Caption
Scheme 1 Optimized geometry of reactants (1, 2), product (3) and side product water (4)
Figure 1 Optimized geometry product (3)
[21]

ACCEPTED MANUSCRIPT
1
Figure 2 Experimental H NMR spectrum of (3) in CDCl solvent
3
[22]

ACCEPTED MANUSCRIPT
13
Figure 3 experimental C NMR spectrum of (3) in CDCl solvent
3
[23]

ACCEPTED MANUSCRIPT
Figure 4 Experimental mass spectrum
Figure 5 Experimental UV-Visible spectrum
[24]

ACCEPTED MANUSCRIPT
Figure 6 Comparison between theoretical and experimental IR spectra for (3)
Figure 7 Molecular electrostatic potential (ESP) map of (3)
[25]

ACCEPTED MANUSCRIPT
Figure 8 HOMO-LUMO Transitions
[26]

ACCEPTED MANUSCRIPT
Scheme :
Scheme 1: The above scheme showed synthetic pathway of N-(4-oxo-2 phenylquinazolin-3(4H)-
yl)-1H-indole-2-carboxamide 3 Where (1) & (2) indicates reactants and 3 is product and 4 is side
product in the form of water.
HIGHLIGHTS
•
•
All Experimental spectral data have good agreement with theoretical data.
Lower value of Global electrophilicity index (ω) represents compound 3 to be a strong
nucleophile.
•
•
First hyperpolarizability (β0) of 10.2254 ×ꢀ10ꢁꢂꢃꢄꢅꢆ shows good NLO response.
Various electronic transition in compound 3 predicted with the help of TD-DFT/B3LYP 6-
3
1(d,p) and Cam-B3LYP/6–31G(d,p) set.
•
MESP map is responsible for prediction of both electrophilic and nucleophilic reactive
behavior.
[27]

ACCEPTED MANUSCRIPT
Table-4 Calculated and experimental electronic excitations for (3): E / eV, oscillatory strength (f), (λmax / nm) at
TD-DFT B3LYP/6–31G(d,p) and Cam-B3LYP/6–31G(d,p) level
B3LYP/6-31G(d,p)
Excitations
9→100 (H→L)
8→100 (H-1→L)
solvent
λmax
λmax
E (eV)
(f)
Assignment
Exp.
calcd.
318.56
326.45
gas
3.8920 0.1040
3.7979
9
9
CHCl3
322
π→π*
0
.1236
gas
308.74
4.0158 0.3606
*
π→π
CHCl3
gas
284
297
308.22
292.86
4.0226 0.2045
4.2738 0.1946
*
9
9
8→102 (H-1→L+2)
3→100 (H-6→L)
π→π
CHCl3
gas
298.13
249.72
4.3050 0.1946
4.9650 0.1534
*
n→π
CHCl3
gas
240
322
284
297
240
252.06
4.9583 0.1347
4.3602 0.5603
4.4151 0.2905
4.6806 0.2383
5.4108 0.1052
Cam-B3LYP/6–
1G(d,p)
99→100 (H→L)
284.35
π→π*
π→π*
π→π*
n→π*
3
98→100 (H-1→L)
2
80.82
iop(10/74=10)
scrf=pisalr
9
9
8→102 (H-1→L+2)
3→100 (H-6→L)
297.53
229.14
td=noneq
Cam-B3LYP/6–
99→100 (H→L)
322
284
297
240
284.50
280.95
277.13
229.21
4.3580 0.5667
4.4130 0.2895
4.6765 0.1091
5.4092 0.2379
π→π*
π→π*
π→π*
n →π*
3
1G(d,p)
98→100 (H-1→L)
iop(10/74=10)
scrf=pisalr
td=noneq
98→102 (H-1→L+2) CHCl3
93→100 (H-6→L)

ACCEPTED MANUSCRIPT
Table 5. Experimental and theoretical [calculated at B3LYP/6–31G(d,p) level] vibrational wavenumbers
–
1
-1
of (3) and their assignments: Wavenumbers ( / cm ), intensity (K mmol ).
Exp. Assignment (PED) ≥ 5 %
unscal.
scaled Exp.
3119 3400
3114
IRin
3
3
246
241
0.18
ν(N22H40)(98)
19.29 ν(C3H32)(40)ν(C6H33)(14)-(δas-R1)(13)-ν(C16C17)(12) ν(C2H31)(8)
ν(C1H30)(7)
3
3
1
1
1
216
208
698
687
670
3090 3036 30.97 ν(C26H42)(42)-ν(C29H45)(27)-ν(C28H44)(22)ν(C27H43)(8)
3082 2926 14.06 ν(C15H36)(47)-ν(C17H38)(45)ν(C18H39)(4)
1631 1765
57.9
ν(C10O11)(43)ν(C19O21)(15)-ν(C5C10)(9)(δtrigonal-R2)(5)
1620 1610 441.22 ν(C19O21)(39)-ν(C10O11)(13)-ν(C19C20)(9)-δ(N12H34)(7)
1604
1596
74.61 ν(C1C6)(16)-ν(C2C3)(13) ν(C3C4)(13)-ν(C5C6)(10)-(δas-R1)(7)
δ(C1C6H33)(6)ν(C5C10)(5)-δ(C3C4H32)(5)
-
1
661
640
5.81
ν(C14C15)(20)ν(C17C18)(19)(δas- R3)(9)-ν(C13C14)(6)-
δ(C14C15H35)(6) δ(C13C18H39)(5)-ν(C13C18)(5)-ν(C16C17)(5)
1
1575 1571 24.95 ν(C16C17)(19)-ν(C15C16)(17)-ν(C13C18)(14)ν(C13C14)(12)
δ(C16C17H37)(10)-(δas- R3)(9)
1538 1540 295.16 ν(C7N8)(46)-ν(C8C13)(8)-ν(C4N7)(7)(δas-R2)(5)
-
1
601
585
1
1523
180.87 ν(C20C25)(29)-ν(C19O21)(10)-ν(C19C20)(8)-ν(C23C26)(8) δ(as-R4)(7)
δ(C20C25H41)(6) -δ(C27C28H43)(5)
-
1557
1496
106.72 (ρ– N9N12H34)(15) δ(C14C15H36)(10) δ(C13C18H39)(9)
δ(C17C18H38)(8)-δ(C14C15H35)(6)-δ(N12H34)(5)ν(C15C16)(5)
-ν(C13C14)(5)
1
549
521
1488 1410 132.27 (ρ– N9N12H34)(44)-δ(N12H34)(14)ν(C19N12)(7)
1
1461
117.79 δ(C1C6H33)(20)-δ(C3C4H32)(19) ν(C4C5)(14)-ν(C4N7)(7)
δ(C1C2H30)(5)
-
ν(C2C3)(5)
ν(C27C28)(12)-ν(C20N22)(10)ν(C24C29)(9)-ν(C28C29)(7)ν(C19C20)(7)
ν(C23C24)(6)-δ(as-R4)(6)δ(C28C29H44)(5)ν(C23C26)(5)-ν(C26C27)(5)
1427
1400
1389
1371
1345
1334
23.5
-
42.25 δ(C28C29H44)(12) -δ(C20C25H41)(10) -δ(C23C26H42)(10)-
ν(C24C25)(9) 1ν(C10O11)(7)-ν(C26C27)(6)ν(C20N22)(5)
65.67 ν(C4C5)(15) ν(C1C6)(12) ν(C2C3)(11)-ν(C5C6)(10)-ν(C3C4)(9)-
ν(C1C2)(8) δ(C14C15H35)(8) δ(C13C18H39)(6)
1
383
368
1329
1315
17.44 ν(C8N9)(15)-ν(C8C13)(13)-ν(N9N12)(8) δ(C13C18H39)(7)
12.13 ν(C13C18)(18)-ν(C13C14)(16)ν(C16C17)(11)ν(C14C15)(11)
1
-ν(C15C16)(10)-ν(C17C18)(9)