Accepted Manuscript

DFT, spectroscopic studies, NBO, NLO and Fukui functional analysis of 1-(1-(2,4-
difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylidene) thiosemicarbazide

Adway Ouseph Zacharias, Anitha Varghese, K.B. Akshaya, M.S. Savitha, Louis
George

PII: S0022-2860(18)30002-4
DOI: 10.1016/j.molstruc.2018.01.002
Reference: MOLSTR 24724

To appear in: Journal of Molecular Structure

Received Date: 31 May 2017

Revised Date: 8 December 2017
Accepted Date: 2 January 2018

Please cite this article as: A.O. Zacharias, A. Varghese, K.B. Akshaya, M.S. Savitha, L. George,
DFT, spectroscopic studies, NBO, NLO and Fukui functional analysis of 1-(1-(2,4-difluorophenyl)-2-
(1H-1,2,4-triazol-1-yl)ethylidene) thiosemicarbazide, Journal of Molecular Structure (2018), doi: 10.1016/
j.molstruc.2018.01.002.

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 ACCEPTED MANUSCRIPT

DFT, spectroscopic studies, NBO, NLO and Fukui functional analysis of 1-

(1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylidene)
thiosemicarbazide
Adway Ouseph Zacharias, Anitha Varghese*, Akshaya K B, Savitha M S, Louis George
Department of Chemistry, Christ University, Bengaluru-560029, India.

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 ACCEPTED MANUSCRIPT
DFT, spectroscopic studies, NBO, NLO and Fukui functional analysis of 1-
(1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylidene)
thiosemicarbazide
Adway Ouseph Zacharias, Anitha Varghese*, Akshaya K B, Savitha M S, Louis George
Department of Chemistry, Christ University, Bengaluru-560029, India.

Abstract

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A novel triazole derivative 1-(1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylidene)
thiosemicarbazide was synthesized and subjected to density functional theory (DFT) studies

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employing B3LYP/6-31+G(d,p) basis set. Characterization was done by FT-IR, Raman,
mass, 1H NMR and 13
C NMR spectroscopic analyses. The stability of the molecule was

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evaluated from NBO studies. Delocalization of electron charge density and hyper-
conjugative interactions were accountable for the stability of the molecule. The dipole

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moment (µ), mean polarizabilty (
α) and first order hyperpolarizability (β) of the molecule
were calculated. Molecular electrostatic potential studies, HOMO-LUMO and
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thermodynamic properties were also determined. HOMO and LUMO energies were
experimentally determined by Cyclic voltammetry.
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Keywords: Density Functional Theory, HOMO-LUMO, Molecular Electrostatic Potential,

Thiosemicarbazide and Fukui Function.
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1. Introduction
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Combating antifungal resistance is turning out to be a cause of great concern among the
scientific fraternity. The long term and unrestricted use of antibiotics and corticosteroids
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have resulted in the evolution of virulent strains of poisonous fungi that have proven to be
extremely difficult to eliminate through commercially available antifungal drugs. In order to
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effectively eliminate human pathogenic fungi genera such as Aspergillus and Candida, that
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exhibit antifungal resistance, it is essential to develop novel drug candidates that have potent
antifungal activity. The antifungal drugs that are employed for clinical use are classified
under three categories: pyrimidines, polyenes and azoles. Among these three, azoles have
turned out to be one of the most widely studied groups due to their superior chemical and
medicinal properties. 1,2,4-triazole derivatives possess important pharmacological activities
such as antifungal and antiviral activities [1].

* Corresponding author. Tel: +91 9448912750; Fax: +918040129000

E-mail address: anitha.varghese@christuniversity.in

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Fluconazole, a popular and effective antifungal agent is an example of such a compound
containing 1,2,4-triazole residues [2]. The highly desirable features of the azole antifungal
drugs are its broad spectrum of activity against common fungal pathogens, limited toxicity,
ease of administration and high therapeutic index [3]. Structure activity relationship studies
of triazole antifungal agents reveals that the presence of 1,2,4 triazole ring and 2,4 difluoro
substituted phenyl group are paramount to the exhibition of effective antifungal activity.

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In the present work, a novel 1,2,4 triazole difluorophenyl thiosemicarbazide derivative, 1-(1-
(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylidene) thiosemicarbazide [DFPTET] was

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synthesized and its geometric and spectroscopic characterization along with thermodynamic
properties have been studied at the Density Functional Theory (DFT) level. The accuracy of

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the theoretical data generated has been corroborated by experimental data especially with
regard to the results pertaining to IR and NMR spectral studies. Many reports have

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commended the success of DFT in comparison to other conventional methods, in computing
molecular and chemical properties such as geometries, harmonic frequencies and energies
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[4-6]. DFT approach is found to be the best compromise between accuracy and
computational cost in comparison to other conventional methods [7].
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In this paper, the vibrational spectral studies of the novel compound have been analysed on
the basis of calculated potential energy distribution (PED) [8]. Natural bond order (NBO)
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analysis was performed using DFT approach to study the redistribution of electron density in
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various bonding and antibonding orbitals in addition to which E(2) energies have been
calculated. The interactions between the bonding and antibonding orbitals were used to
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explain the transfer of electron density. The energies associated with the highest occupied
molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were
determined, using which, the HOMO-LUMO energy gap was calculated. HOMO-LUMO
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energies and their gap was also determined experimentally by cyclic voltammetry. This
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energy gap is an important parameter as it reveals the stability of the molecular structure [9].

2. Materials and Methods

2.1 Experimental
All chemicals and solvents used were obtained from commercial sources. The progress of all
reactions was monitored by Thin Layer Chromatography (TLC). It was carried out using
Merck made silica gel 60 F254 plates with the solvent system ethyl acetate/hexane (3:2).
The product formed was characterised using different spectroscopic studies. 1H and 13
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NMR spectra was recorded on 400 MHz Bruker NMR spectrometer using DMSO as a
solvent and chemical shift values were recorded relative to tetramethylsilane (TMS) as an
internal standard. IR spectrum was recorded using Bruker alpha-T ATR/ FTR spectrometer.
Raman spectrum was recorded using LabRAM HR Raman spectrometer. Mass spectrum
was recorded by LC-MSD-Trap-XCT Plus mass spectrophotometer. HOMO and LUMO
energies were experimentally determined using CH 180 Electrochemical analyzer.

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2.2 Synthesis
DFPTET was prepared by treating 1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone

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with thiosemicarbazide in the presence of few drops of glacial acetic acid followed by
refluxing for 5-6 hours. The product obtained was cooled and isolated by filtering and was

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recrystallized from ethanol. The melting point of the product was found to be 210 0C. The
scheme for the synthesis of DFPTET has been depicted in Fig. 1.

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Fig. 1. Synthesis of DFPTET

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2.3 DFT Modelling

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DFT studies were performed using Gaussian 09W software package [10], on a Pentium
core-i3 processor. The molecule was initially modelled using graphic user interface
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GaussView 5.0 [11] at the semi-empirical PM6 level. The geometries obtained from this
level of optimization were then subjected to DFT studies employing B3LYP functional
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using 6-31G (d,p) basis set. The rationale behind choosing this basis set was to allow the
atomic orbitals (A.O)’s to get polarized, where the p type functionals added onto the
hydrogen atoms and d type functionals added on to all the other atoms [12]. Diffuse
functionals were added onto atoms other than hydrogen since the molecule consists of atoms
like nitrogen, sulphur and fluorine which contain lone pairs of electrons. The vibrational
frequencies pertaining to the fundamental modes were computed and the absence of
imaginary frequencies confirmed that optimization calculations performed earlier, resulted
in a structure associated with minimum potential energy and hence maximum stability. A
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stability check calculation revealed that a true minimum was obtained on the potential
energy surface. The assignments corresponding to the normal vibrational modes were
obtained from the PED matrix using vibrational energy distribution analysis (VEDA)
program [13] and these vibrations were visualized using GaussView 5.0. The NLO
properties of DFPTET such as dipole moment, polarizability and first order
hyperpolarizability were also determined. The NBO calculations [14] were performed using

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NBO 3.1 program as implemented in the Gaussian 09W [10] software package at the
DFT/B3LYP level in order to comprehend the hyperconjugation.

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2.4 Determination of HOMO-LUMO energies by using cyclic voltammetry

The frontier molecular orbital (FMO) energies in ground state were calculated

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experimentally by cyclic voltammetry. For experimental measurements of HOMO and
LUMO, ferrocene was used as an internal standard reference. The potential values obtained

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for ferrocene/ferrocenium redox couple were converted to vacuum scale using the standard
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approximation that ferrocene/ferrocenium HOMO level is – 4.8 eV. Cyclic voltammograms
of internal standard ferrocene and DFPTET have been recorded in acetonitrile using lithium
perchlorate as the supporting electrolyte. A three electrode system consisting of platinum
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working electrode, platinum counter electrode and Ag/AgCl as reference electrode at

ambient temperature was set up. HOMO and LUMO energies were calculated using
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oxidation and reduction potential values, as given below.

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E = −[E
− E   + 4.8] eV (1)

E = −[E  − E   + 4.8] eV (2)

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E = [E − E ] eV (3)

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Where, EHOMO and ELUMO are the energies of HOMO and LUMO, Eox and Ered are oxidation
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potential and reduction potential of the molecule of interest, Eferrocene is the reduction
potential of internal standard ferrocene. The standard value of reduction potential for
ferrocene-ferrocenium ion is 4.8. The electrochemical gap between the HOMO and LUMO
energy levels can be represented as Eg.

2.5 Global reactivity descriptors

Electronegativity (χ), hardness (η), softness (S) and electrophilicity index (ω) serve as
global reactivity parameters with regard to Density Functional Theory. Using B3LYP/6-
32+G(d,p) method, HOMO and LUMO energies, energy gap (∆E), absolute
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electronegativity (χ), absolute hardness (n) and electrophilicity index (ω) of DFPTET were
calculated and listed in Table 6. Koopman’s theorem [15] clearly states that the electron
affinity (EA) and ionisation potential (IP) of a molecule can be expressed in terms of its
HOMO and LUMO orbital energies.

Ionization potential (IP) -EHOMO (4)

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Electron affinity (EA) -ELUMO (5)

Mulliken [16] defined electronegativity as the average of ionization potential (IP) and

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electron affinity (EA).

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Electronegativity (χ) = (IP + EA)/2 (6)

The energy gap between the HOMO and LUMO of a molecule is directly related to its

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hardness. A large energy gap (∆E) suggests a harder molecule [17]. Chemical hardness can
be calculated as follows:
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Chemical hardness (η) IP − EA/2 (7)
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Global hardness is found to be the inverse of global softness [18]

Softness (S) = 1/ (8)

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Chemical potential is defined by Parr and Pearson [19] as the characteristic of

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electronegativity of molecules.

Chemical potential (µ) = -(IP-EA)/2 (9)

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The global electrophilicity index (ω) as defined by Parr et al [20] measures the propensity of
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a species to accept electrons and is related to the electronic chemical potential (µ) and
chemical hardness (η)
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Electrophilicity index (ω) = ! " /η (10)

3. Results and discussion

3.1 Molecular geometry

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Fig. 2. The optimised molecular structure of DFPTET
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The numbering of the atoms of DFPTET is represented in Fig. 2. The calculated bond
lengths and bond angles are tabulated as seen in Table 1. C-H bond lengths vary between
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1.0789-1.0969 Å. Several researchers [21, 22] have suggested that changes in the bond
length of C-H bond on substitution were due to difference in the charge distribution on
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carbon atom of the benzene ring. In this case, since the fluorine atoms (F10, F11) are
electron withdrawing groups, there is a reduction in the electron density of phenyl ring
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carbon atoms. These phenyl ring carbon atoms distort the valence electron cloud of the
hydrogen atoms bonded to them, resulting in an increase in the C-H force constant and a
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decrease in the C-H bond length [23]. The C-C bond lengths vary from 1.3893-1.5239 Å.
The N-H, N-C and N-N bond lengths have maximum values of 1.0114 Å, 1.4474 Å and
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1.3600 Å respectively. The calculated S-C bond length was found to be 1.6756 Å which is
intermediate between single (1.820 Å) and double (1.560 Å) bond values involving carbon
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and sulphur [24]. This can be explained by resonance that is observed between the amino
group and the sulphur atom bonded to the alpha carbons (C15). Due to this, there is a partial
double bond character that is being exhibited, as reflected in the calculated C-S bond length.
The optimized geometrical parameters make for a good approximation and serve as the
foundation upon which the vibrational frequencies are calculated.

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Table 1
Optimized geometrical parameters of DFPTET by DFT B3LYP/6-31+G(d,p)
Bond length Values (Å) Bond angle Values Values
(deg) (deg)
C1-C2 1.3923 C2-C1-C6 118.222 C6-C1-C2-C3 -0.015
C1-C6 1.3948 C2-C1-H7 120.083 C6-C1-C2-F11 -179.976
C1-H7 1.0833 C6-C1-H7 121.694 H7-C1-C2-C3 179.828
C2-C3 1.3896 C1-C2-C3 122.668 H7-C1-C2-F11 -0.092

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C2-F11 1.3494 C1-C2-F11 118.998 C2-C1-C6-C5 -0.071
C3-C4 1.3893 C3-C2-F11 118.332 C2-C1-C6-H9 179.437
C3-H8 1.0833 C2-C3-C4 117.113 H7-C1-C6-C5 -178.994

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C4-C5 1.4003 C2-C3-H8 121.68 H7-C1-C6-H9 -0.443
C4-F10 1.3549 C4-C3-H8 121.204 C1-C2-C3-C4 0.017
C5-C6 1.4084 C3-C4-C5 123.437 C1-C2-C3-H8 179.603

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C5-C12 1.4924 C3-C4-F10 117.731 F11-C2-C3-C4 179.762
C6-H9 1.0858 C5-C4-F10 118.829 F11-C2-C3-H8 -0.436
C12-N13 1.2856 C4-C5-C6 116.738 C2-C3-C4-C5 0.068
C12-C21 1.5239 C4-C5-C12 122.032 C2-C3-C4-F10 179.651

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N13-N14 1.3526 C6-C6-C12 121.213 H8-C3-C4-C5 -179.519
N14-H16 1.0162 C1-C6-C5 121.819 H8-C3-C4-F10 0.065
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N14-C15 1.3800 C1-C6-H9 119.227 C3-C4-C5-C6 -0.147
C15-S17 1.6756 C5-C6-H9 119.227 C3-C4-C6-C12 -178.705
C15-N18 1.3460 C5-C12-N13 125.278 F10-C4-C5-C6 -179.728
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N18-H20 1.0114 C5-C12-C21 116.873 F10-C4-C5-C12 1.719

N18-H19 1.0071 C13-C12-C21 117.795 C4-C5-C6-C1 0.147
C21-H30 1.0929 C12-C13-N14 120.699 C4-C5-C6-H9 -179.362
C21-H29 1.0969 N13-N14-C15 121.105 C12-C5-C6-C1 178.712
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C21-N22 1.4474 N13-N14-H16 122.542 C12-C5-C6-H9 -0.797

N22-N23 1.3600 C15-N14-H16 116.145 C4-C5-C12-N13 -120.597
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N23-C24 1.3252 N14-C15-N18 115.341 C4-C5-C12-C21 -116.354

C24-H28 1.0807 S17-C15-N18 125.074 C5-C12-N13-N14 3.622
C24-N26 1.3652 C15-N18-H19 118.102 C21-C1-N13-N14 -179.132
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N26-C25 1.3229 C15-N18-H20 120.789 C5-C12-C21-N22 -176.338

C25-H27 1.0812 H19-N18-H20 120.799 C5-C12-C21-H29 61.821
C25-N22 1.3533 C12-C21-N22 114.016 C5-C12-C21-H30 -55.888
C12-C21-H29 109.357 C12-N13-N14-C15 178.878
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C12-C21-H30 109.793 C12-N13-N14-H16 4.298

N22-C12-H29 108.646 N13-N14-C15-S17 -178.966
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N22-C21-H30 107.322 N13-N14-C15-N18 1.855

H29-C21-H30 107.491 H16-N14-C15-S17 -4.055
C21-N22-N23 120.748 H16-N14-C15-N18 176.766
C21-N22-C25 129.453 N14-C15-N18-H19 -178.260
N23-N22-C25 109.489 N14-C15-N18-H20 -4.583
N26-C24-H28 123.278 S17-C15-N18-H19 2.613
N22-C25-N26 110.458 S17-C15-N18-H20 176.291
N22-C25-H27 123.13 C12-C21-N22-N23 90.016
N26-C25-H27 126.411 C12-C21-N22-C25 -82.991
C24-N26-C25 102.536 H29-C21-N22-N23 -147.752
H29-C21-N22-C25 39.241

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H30-C21-N22-N23 -31.807
H30-C21-N22-C25 155.186
C21-N22-N23-C24 -0.706
C21-N22-C25-N26 174.388
C21-N22-C25-H27 -5.821
N23-N22-C25-N26 0.762
N23-N22-C25-H27 -179.446
N22-N23-C25-N26 0.450
N22-N23-C24-N26 -178.953

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N23-C24-N26-C25 -0.014
H28-C24-N26-C25 179.377
N22-C25-N26-C24 -0.448

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H27-C25-N26-C24 179.769

3.2 Vibrational Analysis

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1-(1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethylidene)thiosemicarbazide contains 30
atoms as depicted in Fig. 2. The modes of vibrations that have been classified as stretching

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υ, in-plane bending β and out of plane bending γ modes and torsion τ. The molecule is
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observed to have C1 point group symmetry. The vibrational assignments corresponding to
each vibrational mode have been documented in Table 2. These vibrational assignments
have been applied on the recorded FT-IR and Raman spectra (Fig. 3 and Fig. 4) based on the
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theoretically determined wavenumbers by B3LYP with 6-31+G(d,p) along with their PED
values. The stability of the optimized structure is evident since all the calculated
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wavenumbers are positive. There are deviations that are found between the calculated
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frequencies and the experimentally observed frequencies due to the neglect of vibrational
anharmonicity, incompleteness of the basis set and electron correlation (Fig. 5 and Fig. 6)
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[25, 26]. The calculated frequencies are harmonic in nature while the experimental
frequencies are anharmonic. This is the main reason for deviations with regard to methylene
groups. Deviations pertaining to other groups arise due to the approximations employed in
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the computational method. In order to address these systemic errors, the calculated
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frequencies were scaled by a compatible scaling factor of 0.961, thereby reducing the
deviation between theoretical and experimental results. It is also acknowledged that
discrepancies could arise due to lattice effects of DFPTET when studied in its solid phase,
while theoretical calculations were performed in the gaseous phase, as a result of which low
frequency values will not be reliable.

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Fig. 3. Experimental and calculated FT-IR of DFPTET

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Fig. 4: Experimental and calculated FT-Raman of DFPTET

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Experimental and calculated DFT-B3LYP/6-31+G(d,p) levels of vibrational frequencies (FT-IR spectrum) of DFPTET.
Experimental frequencies Calculated with B3LYP/6-31+G(d,p)
Sl.No Vibrational Assignments along with % of PED
-1 -1 -1 -1
FT-IR (cm ) FT-Raman (cm ) Unscaled (cm ) Scaled (cm ) IR intensity Raman activity

1 3543 (w) 3739 3595 110.24 54.78 νas N-H (100)

2 3475 (w) 3581 3441 69.06 149.94 νs N-H (100)
3 3440 (w) 3545 3407 28.05 150.88 νs Ν−Η (99)
4 3135 (w) 3146 (m) 3276 3148 1.99 143.16 νs C-H (94)
5 3137 (w) 3140 (w) 3268 3140 1.41 37.95 νas C-H (94)
6 3125 (w) 3119 (w) 3239 3113 2.49 152.32 νs C-H (99)
7 3109 (m) 3231 3105 0.67 133.66 νs C−Η (94)

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8 3203 (vw) 3086 (w) 3202 3077 0.63 31.75 νas C−Η (94)
9 3010 (m) 3125 3003 0.46 74.69 νas C-H (100)
10 2912 (w) 2908 (m) 3054 2935 17.7 230.47 νs C-H (100)
11 1612 (vs) 1618 (vs) 1689 1623 19.55 632 νs N=C (78)

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12 1592 (s) 1590 (w) 1659 1594 145 113 νs C=C (42)
13 1570 (w) 1555 (w) 1629 1565 61.47 12.61 νas C=C (61)
14 1580 (m) 1623 1559 227.65 9.58 δ N=H (72)
15 1518 (s) 1552 1491 68.63 2.861 νas N=C (46)

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16 1470 (s) 1532 1472 96.48 20.09 νs C=C (12) δ CCH (43)
17 1448 (vs) 1438 (vw) 1513 1454 473.39 29.88 νs N=C (15) δ HNN (57)
18 1413 (w) 1482 1424 14.61 21.81 νas N=C (18) τ HCCC (39)
19 1467 1410 37.67 13.94 νσ Ν=C (27) β ΗCΗ (35)

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20 1456 1399 39.38 8.23 νas C=C (30) β HCC (12)
21 1451 1394 81.71 25.4 νas N=C (53) δ HNH (10)
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22 1345 1345 8.12 24.91 νs N-C (65)
23 1330 (w) 1389 1335 43.45 52.7 δ HCN (32) τ HCCC (26)
24 1270 (m) 1351 1298 2.26 5.83 νas N-C (18) β HCC (21)
25 1289 (m) 1282 (w) 1342 1289 11.66 2.44 νas C-C (60)
37.15 15.06 δ CNN (27) δ NCN (15) δ ΗCN (15)
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26 1231 (m) 1217 (w) 1314 1263

27 1296 (m) 1286 (w) 1299 1248 55.99 3.38 νas N-C (12) ν FC (21) δ HCC (34)
28 1289 (m) 1278 (w) 1294 1243 138.24 121.52 νas C-C (11) δ HCC (11)
29 1282 (m) 1280 (m) 1287 1237 255.07 12.23 δ HNC (26) δ HNN (22) νs (12)
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30 1238 1189 2.56 5.58 β HCN (13)

31 1236 1188 27.14 5.34 β HCN (34)
32 1171 (m) 1194 1147 3.15 3.87 δ HCC (34) νas NC (18) νas N-N (10)
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33 1130 (m) 1171 1125 59.7 5.94 νs N-N (24) δ HCC (18)
34 1168 1122 26.26 12.57 δ HCN (37) δ CNN (43)
35 1162 1117 107.53 19.31 ν N-N (36) β HCC (17)
36 1124 1080 68.16 1.49 δ HCC (34)
δ CCC (11) δ NNC (10)
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37 1089 1046 27.7 14.46

38 1006 (w) 1005 (w) 1035 995 28.74 7.92 νs N-C (17) δ ΝΝ (27)
39 1028 988 45.5 5.82 νs C-C (16) δ HNC (17)
40 984 (vw) 986 948 50 7.44 νas C-C (37) νs F-C (26) δ CCC (12)
0.22 1.79 τ HCCC (82) τ CCCC (12)
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41 974 936
42 971 933 5.63 1.44 δ NCN (49) δ CNN (27)
43 955 918 4.47 2.42 ν NN (20) δ HCC (12) τ HCCC (38)
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44 900 865 8.05 0.11 τ HCNC (84) τ CNNC (10)

45 871 (vw) 874 840 47 0.75 τ HCCC (68) γ FCCC (12)
46 866 832 36.68 0.04 νs N-C (10) νs SC (17) β HCN (11) δ CNN (13)
47 852 819 26.44 1.58 τ HCNC (73) τ NCNN (19)
48 804 (s) 797 (w) 839 806 5.84 2.06 τ ΗCCC (43) τ HCCC (25)
49 810 778 20.33 0.92 νs S-C (20) δ CCN (21)
50 730 (w) 757 728 5.92 9.97 δ CCC (12)
51 735 706 11.5 0.2 δ CCC (18)
52 719 691 0.05 7.78 νas N-C (10) τ CCCC (35)
53 690 663 22.32 0.56 τ HCNC (16) τ CNNC (67)
54 640 (m) 660 634 1.08 0.6 τ HCNC (11) τ NCNN (52)
55 644 619 11.18 6.64 δ CCC (12) γ NCCC (19)
56 648 (w) 641 616 9.91 2.15 τ HNNC (12) τ HNCN (42) γ SNNC (31)
57 608 (m) 631 605 9.15 1.66 τ HCCC (17) τ CCCC (24) γ FCCC (24)
58 580 (m) 601 577 35.52 3.93 δ CCC (10) γ FCCC (15)
59 568 (m) 590 567 2.31 0.69 τ HNCN (34) γ SNNC (52)
60 538 (w) 545 524 17.11 2.53 τ HNNC (47) τ HNCN (10)

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19.02 3.31 νas C-C (10) νas FC (10) δ CCC (19)
62 516 496 24.2 4.73 τ HNNC (13)
63 497 (m) 479 (w) 491 472 3.62 10.81 νas S-C (12) δ (FCC) (32)
64 460 (vw) 470 452 2.12 0.95 τ CCCC (48)
65 444(w) 458 440 11.7 1.97 δ ΝCN (27) δ FCC (13)
66 401 385 10.16 1.23 δ SCN (45)
67 346 (w) 360 346 70.27 3.88 τ HNCN (39) τ NNCC (12)
68 348 334 2.28 0.25 δ CNN (67) τ HCCC (11)
69 338 325 34.59 1.38 δ FCC (12)
70 330 (m) 336 323 14.52 1.87 δ FCC (52)
71 300 (w) 331 299 31.82 0.88 τ HNCN (25) τ NNCC (44)
72 256 246 0.66 1.19 νas C-C (11) δ CCN (15) δ SCN (11)
73 229 (w) 233 224 0.62 2.75 τ CCCC (24) δ FCCC (57)

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74 214 206 11.52 3.68 νas C-C (12) δ NCC (16) δ NCN (19) δ CNN (21)
75 174 167 0.29 1.01 δ CCC (20) τ CCCC (10)
76 145 (vw) 152 146 0.54 0.27 δ CCC (36)
77 120 115 1.22 1.61 δ CNN (11) γ NNC (17) γ CCNN (16)

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78 91 87 2.02 0.96 νas SC (12) τ CNNC (45) τ CNNC (12) γ CCNN (10)
79 56 54 0.86 1.62 τ CCNC (12) τ NCNN (10) τ NCNN (43)
80 50 48 0.27 3.6 τ CCNC (55) τ ΝCΝΝ (12)
81 43 41 0.68 3.03 τ CCCC (45) δ CCC (19)

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82 42 40 1.72 5.65 δ NCC (13)
83 30 29 1.23 4.09 τ CCCC (43)
84 25 24.05 0.6 1.73 τ CCCC (23)

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Abbreviations
ν – stretching, β – in-plane bending, γ – out of plane bending, τ - torsion, vs- very strong, s- strong, m- medium, w-weak, vw- very weak
AN
a-Scaling factor: 0.961 for B3LYP/6-31+G(d,p)
M
D
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C EP
AC

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3.2.1 C-H vibrations

The C-H stretching vibrations of heteroatomic molecules act as a fingerprint for its
identification with peaks usually occurring in the region between 3100-2900 cm-1 .The
frequencies of aromatic sp2 C-H stretching generally occur above 3000 cm-1, which is higher
than the corresponding aliphatic C-H stretching due to the presence of ring strain in aromatic
moieties which means that a greater amount of energy is required to stretch aromatic C-H

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bonds. Since there is a slight overlap between the frequencies of C-H stretching
corresponding to aliphatic and aromatic groups, the calculated C-H stretching frequencies of

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DFPTET do not hold much significance in terms of identification of the molecule.
B3LYP/6-31+G(d,p) method generated C-H stretching frequencies, 3140 cm-1 which was

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close to the experimental value of 3137 cm-1, and 3148 cm-1 which is in reasonably good
agreement with the experimental value of 3135 cm-1. FT-Raman values for C-H stretching

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correspond to bands of medium intensities at 2908 cm-1, 3086 cm-1, 3109 cm-1, 3140 cm-1
and 3146 cm-1. All the modes of vibration corresponding to this class of stretching
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contributed between 94 percent and 100 percent of PED.
M

3.2.2 C-C vibrations

Unlike in case of C-H stretching, G. Ramachandran et. al [27] have stated that C-C aromatic
D

stretching gives rise to characteristic peaks in the IR spectrum, spread over a range between
1600-1400 cm-1. DFPTET exhibits bands at 1594 cm-1, 1565 cm-1 and 1472 cm-1 in the
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theoretical FT-IR spectrum. A majority of these bands are in good agreement with the
experimentally observed peaks of medium and strong strength. There are a few C-C
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aliphatic vibrations that occur at frequencies 1289 cm-1 and 1243 cm-1, whose peaks are of
intensities that are lower than those observed for C-C aromatic vibrations. Although the
C

contributions of these vibrations to PED is almost the same in both aliphatic and aromatic
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cases, ranging from 30-60 percent, it is also observed that there are many instances of HCC
and CCC in and out of plane bending, for which there is an excellent correlation between the
computed values and the experimental values. These out of plane bending vibrations have
also been accounted for by FT-IR vibrations at 577 cm-1,620 cm-1 and 879 cm-1 respectively.
The contribution of these bending vibrations is generally seen to be less than 16 percent of
PED.

3.2.3 N-H vibrations

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The population of N-H bands in the FT-IR spectrum are not as large as C-H or C-C bands.
This is partly because of the fact that these bands occur at very high frequencies due to
greater bond strength associated with N-H bonds. There are two bands at 3595 cm-1, 3441
cm-1 and 3407 cm-1 that are observed in case of the computed FT-IR spectrum. In terms of
potential energy distribution (PED) contributions, each N-H vibration contributed 99-100
percent .Torsion vibrations were observed in the case of HNCN and HNNC bonds at 567

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cm-1 which was matched reasonably well with an experimental value of 568 cm-1. There
were also bands predicted at 567 cm-1 and 524 cm-1 corresponding to torsion vibrations

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which contributed 34 – 47 percent to the PED respectively. FT-Raman corresponding to
HNCN and HNNC torsion vibrations occur at 346 cm-1 and 648 cm-1 respectively.

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3.2.4 C-N vibrations

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The identification of C-N vibrations is not very straightforward since there is a possibility of
the presence of bands belonging to various functional groups being located in the same
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frequency range. Silverstein et al. [28] ascertained that C-N bands typically occur between
1342 cm-1 and 1266 cm-1 for aromatic amines and C-N stretching vibrations being confined
M

to a frequency range of 1598-1411 cm-1. The C-N stretching bands for DFPTET were
obtained at 1270 cm-1. The B3LYP/6-31+G(d,p) method yielded a comparable result, 1298
D

cm-1. The potential energy distribution (PED) for these bands was determined to be 36
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percent. FT-Raman vibrational analysis gave comparatively strong peak pertaining to C=N
symmetric stretching at 1618 cm-1 and several weak to medium intensity peaks
corresponding to HNC in plane bending at 1280 cm-1, 1286 cm-1 and 1217 cm-1.
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3.2.5 C-F, C-S and ring vibrations

C

There are two fluorine atom substituents situated on the benzene ring present in DFPTET.
AC

One is in the ortho position while the other is in the para position with respect to the ipso
carbon atom. The experimentally obtained FT-IR C-F band was located at 1296 cm-1 while
the theoretical calculations predicted a value of 1248 cm-1 which is quite close. FT-Raman in
turn displayed C-F symmetric stretching at 1286 cm-1 and FCCC out of plane bending at 871
cm-1. In addition to this band, there were several more that were predicted in the theoretical
FT-IR spectrum at 577 cm-1 and 605 cm-1, the corresponding bands observed in the
experimental FT-IR were 580 cm-1 and 608 cm-1 respectively. There is one C-S bond
situated in close proximity to the azole ring which gave out of plane bending SNNC

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vibration at 568 cm-1 experimentally which was comparable to a theoretical frequency of
567 cm-1. There were ring vibrations observed in the spectrum obtained from B3LYP/6-
31+G(d,p) method calculated at 1335 cm-1 which was in good agreement with an
experimental value of 1330 cm-1. The presence of substituents on the phenyl ring will affect
the position of its corresponding band in the FT-IR spectrum. Small deviations between
experimental and theoretical data may be attributed to changes in the force constant (k) and

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reduced mass ratio due to the extent of mixing between ring and substituent groups.

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U SC
AN
M
D

Fig. 5. FT-IR spectrum correlation graph

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C EP
AC

Fig. 6. FT-Raman correlation graph

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3.3 Mass spectrum

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U SC
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M

Fig. 7. Predicted mass fragmentation pattern of DFPTET

D

The mass spectrum of the synthesized triazole thiosemicarbazide derivative is recorded (S1).
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The fragmentation of the monoisotopic ion [M+H]+ (m/z, 297) gave rise to peaks observed
at m/z 280, 270, 228, 168 and 154 when spectrophotometer was run in positive scan mode.
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The fragmentation pattern observed was attributed to the cleavage of C-N, N-N and C-C
bonds. The proposed fragmentation pattern is depicted in Fig. 7.
C

3.4 NMR studies

AC

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Fig. 8. 13C NMR spectra of DFPTET

PT
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Fig. 9. 1H NMR spectra of DFPTET
13
The experimental and theoretical C NMR and 1H NMR spectra are represented in Fig. 8

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and Fig. 9 respectively. The gauge-included atomic orbital (GIAO) 1H NMR and 13C NMR
of DFPTET were computed using B3LYP/6-31+G(d,p) method that was used to compute the

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optimized geometries with tetramethylsilane (TMS) as a reference. This compound was
chosen as a reference since the protons of its methyl groups are shielded to a greater extent
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when compared to most other compounds. The experimental and theoretical chemical shifts
are tabulated in Table 3. The numbering system that was adopted to label atoms is
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represented in Fig. 2. There are many signals that are observed both in the theoretical and
13
experimental C NMR spectrum with chemical shift values ranging between 100-165 ppm
D

due to the presence of aromatic carbons. The signal at 0 ppm in 1H NMR and 13
C NMR is
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due to TMS and should be ignored.

Table 3.
The experimental and predicted 1H and 13C NMR isotopic chemical shifts of DFPTET.
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Atom Experimental (ppm) Calculated (B3LYP/6-31+G(d,p) (ppm)

C1 104.06 91.86
C

C2 145.54 148.80
C3 105.00 105.50
AC

C4 151.73 154.02
C5 103.80 100.28
C6 120.53 124.71
C12 132.23 135.12
C15 164.64 167.85
C21 152.45 152.24
C24 151.64 152.96
C24 151.64 152.96
C25 120.37 121.23
H7 11.08 9.16
H8 7.31 7.37
H9 7.44 7.57
H16 7.90 8.32

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H19 5.29 6.10
H20 7.09 6.77
H27 8.43 8.55
H28 10.19 9.09
H29 7.86 7.84
H30 7.81 7.87

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3.5 Natural bond order analysis

NBO analysis is an efficient method that can be used to study intra and inter molecular

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bonding, interaction among bonds and also provides a convenient means to investigate
charge transfer or conjugative interactions in a molecular system [29] It can be used to

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estimate the transfer of electron density from the bonding orbitals to the antibonding
orbitals, and study about how these interactions contribute to the stability of the molecule. In
Table 4, there are three categories of natural bond orbital (NBO) interactions, the Lewis type

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(s and p bonding or lone pair) orbitals, the valence non-Lewis (acceptors, formally unfilled)
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orbitals and the Rydberg NBOs [30]. E(2) denotes the second order energy of interaction
between the donor and acceptor orbitals in DFPTET. The E(2) values for interactions
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between bonding and antibonding orbitals is found to be the highest for donors σ C2-C3 and
σ C1-C6 corresponding to acceptors σ* C4-C5 and σ* C2-C3, having E(2) values of 24.28
D

kcal/mol and 23.93 kcal/mol respectively. These interactions contribute greatest to the
stabilization of the molecule. Similarly interactions involving lone pairs and vacant
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antibonding orbitals such as LP(1) N18 → σ* C15-S17 and LP(1) N22 → σ* C25-N26 have
high E(2) values of 60.86 kcal/mol and 52.29 kcal/mol respectively contribute towards
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weakening of the bond associated with antibonding orbital.

C

Table 4.
Second order perturbation theory analysis of Fock matrix in NBO basis for DFPTET.
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Donor Type ED(i)(e)(e) Acceptor Type ED (j)(e)(e) E(2)a (kcal/mol) E(j)-E(i)b F(i,j)c
(i) (j) (au) (au)

C1-C2 σ 1.9818 C2-C3 σ∗ 0.3733 23.96 0.27 0.073

C2-C3 σ 1.9758 C4-C5 σ∗ 0.4138 24.28 0.28 0.075
F10 LP 1.9213 C4-C5 σ∗ 0.4138 19.38 0.43 0.089
F11 LP 1.9188 C2-C3 σ∗ 0.3733 19.95 0.42 0.089
N14 LP 1.6611 C12-N13 σ∗ 0.2032 32.76 0.28 0.088
N14 LP 1.6611 C15-S17 σ∗ 0.4616 47.01 0.25 0.100
N18 LP 1.7077 C15-S17 σ∗ 0.4616 60.86 0.23 0.111
N22 LP 1.5330 C12-C21 σ∗ 0.0413 17.27 0.64 0.069
N22 LP 1.5330 N23-C24 σ∗ 0.3435 25.95 0.28 0.078

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N22 LP 1.5330 C25-N26 σ∗ 0.3840 52.29 0.27 0.108
C4-C5 σ 1.9748 C12-N13 σ∗ 0.2032 52.89 0.01 0.038
ED- Electron density
a
Energy of hyper conjugative interaction (stabilization energy)
b
Energy difference between donor and acceptor i and j NBO orbital.
c
Fock matrix element between i and j NBO orbital.

3.6 NLO studies

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The first order hyperpolarizability (βtotal) of DFPTET in addition to related properties such as
µ, α and ∆α are evaluated by DFT B3LYP method with 6-31+G(d,p) basis set. Interactions

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between electromagnetic fields in different media gives rise to NLO activity as a

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consequence of changes in phase, frequency, amplitude or other propagation characteristics
from incident fields. NLO properties are useful in studying functions of primary importance
with regard to optical modulation, optical logic, optical memory, optical switching and

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frequency shifting as applications in areas such as signal processing and telecommunications
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[31].

The total dipole moment of an isolated molecule in the presence of an electric field Eiω is
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represented as a Taylor series.

D

μ$ $%& = μ' + α)* E* + β)*, E* E, + (11)

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where α is the linear polarizability, µ0 is the permanent dipole moment and βikj is the first
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hyperpolarizability tensor components. The isotropic linear polarizability is defined as:

α = α

+ α-- + α.. /3 (12)

C
AC

∆0 =2**(-1/2)(011 − 022 " + 022 − 033 " + 033 − 011 " + 6011 "  ∗∗ 1/2 (13)

The first order hyperpolarizability is described as a third rank tensor that can be described by
a 3 x 3 x 3 matrix. The 27 components of 3D matrix can be abridged to 10 components
owing to the Klienman symmetry [32].The components of the first hyperpolarizability can
be resolved from the following equation:

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β) = β))) + Σ)8* 9β)** + β*)* + βjji< (14)

Employing the x, y and z components of β, the magnitude of the first hyperpolarizability

tensor can be estimated by

β$ $%& = β
" + β- " + β. "  ∗∗ 1/2 (15)

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The final equation that is used to reckon the magnitude of β is given by:

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β$ $%& = β

+ β
-- + β
.. " + β--- + β-.. + β

- " + 9β... + β

. + β--. " < ∗∗ 1/2 (16)

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Urea was the first compound to have been subjected to an investigation of NLO properties,

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thereby it is often used as a threshold value for the sake of comparison. The calculated
dipole moment, linear polarizability and hyperpolaizability obtained from B3LYP/6-
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31+G(d,p) are enumerated in Table 5. The value of total dipole moment µtotal and βtotal are
5.0847 D and 1.0576 x 10-30 esu obtained from (DFT) B3LYP/6-31+G(d,p) respectively.
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These values are greater than that of urea (µtotal and βtotal for urea are 1.3732 D and 0.3728 x
10-30 esu) . Mean polarizability (∆α) of DFPTET is found to be 3.1575 x 10-23 esu. The first
D

order hyperpolarizability of DFPTET is approximately three times that of urea, making it a

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viable candidate for future non linear optical studies.

Table 5.
EP

Dipole moment (µ), polarizability (α) and hyperpolarizability (β) of DFPTET.

Parameters B3LYP/6-31+G(d,p)
µx 2.3622
C

µy -3.6398
µz 2.6507
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µtotal 5.0847 D

αxx 127.8234
αxy -7.6567
αyy 143.9540
αyz 0.7204
αzz 120.4086
αxz 3.1708
∆α 3.1575 x 10-23 esu

βxxx 32.3581
βxyy 18.9862

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βxzz 22.3941
βyyy -124.1040
βyzz -9.7342
βyxx 38.5574
βzzz 8.8196
βzxx -42.1848
βzyy 11.7967
βtotal 1.0576 x 10-30 esu

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3.7 Molecular electrostatic potential

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Molecular electrostatic potential (MEP) is related to the electronic density and is a very
useful descriptor in understanding sites for electrophilic and nucleophilic reactions as well as

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hydrogen bonding interactions [27]. MEP is also very useful in the investigation of the
molecular structure with its physiochemical relationships [27, 28]. It provides a visual
method to understand the polarity of the molecule and mapping an electron density

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isosurface with electrostatic potential surface depicts the size, shape, charge density and sites
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of chemical reactivity of the molecule [28]. Potential increases in the order red < orange <
yellow< green < blue. The negative (red, orange and yellow) regions of the MEP pertain to
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electrophilic reactivity. It is seen that the region around the C-S and C-N-C bond of the azole
ring is the most negative potential region (red) and hence this is the region that pertains to
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electrophilic reactivity. On the other hand in the vicinity of the amino group situated alpha to
the C-S bond signifies a positive potential region and is a site for nucleophilic reactivity
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(blue). Thus these sites give information about the region from where the compound can
take part in intermolecular interactions. The MEP of the title compound, DFPTET, is shown
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in Fig.10.
C
AC

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Fig. 10. Molecular electrostatic potential map of DFPTET
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3.8 Frontier Molecular Orbital Analysis by DFT and Cyclic Voltammetry

D

The HOMO and LUMO are crucial to understand the way electron transfer affects the
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stability of a molecule during a chemical reaction [8]. The HOMO is the orbital that
primarily acts as the electron donor and the LUMO is the orbital that largely acts as the
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electron acceptor, and the gap between HOMO and LUMO characterizes the molecular
chemical stability [9]. There is a definite energy value, obtained in electron volts (eV) that is
associated with both HOMO and LUMO. The difference between these energies is called the
C

HOMO-LUMO energy gap, which provides an accurate estimation of the reactivity of a

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molecule. Because of this attribute, these orbitals are also termed as frontier orbitals [26]. As
the difference in energy between the HOMO and LUMO becomes smaller, in other words,
as they approach degeneracy, the molecule becomes more stable. Due to this small energy
gap, electrons are capable of being excited from HOMO to LUMO by supplying energy that
is usually associated with small frequencies.

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PT
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U SC
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M
D
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C EP
AC

Fig. 11. Isodensity plots of frontier molecular orbitals of DFPTET

Fig. 11 depicts the delocalization that is associated with the HOMO and LUMO of DFPTET.
The energy values obtained adopting DFT/6-31+G(d,p) method corresponding to HOMO
was found to be -6.0955 eV and that corresponding to LUMO was observed as -2.0561 eV.
These values give rise to an energy gap of 4.0394 eV which accounts for the strong
delocalization that is observed within the DFPTET molecule. HOMO energy and LUMO
energy of DFPTET (Table 6) with respect to the ferrocene standard reference (4.8 eV) were

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determined. The oxidation and reduction potential of DFPTET was experimentally found to
be Eox = 0.8839 V and Ered= -0.2904 V respectively. Ferrocene has been used as an internal
standard and shows two peaks at 0.36 V and 0.48 V [33]. Therefore, E1/2 (ferrocene) was
equal to 0.42 V which was used in determination of HOMO and LUMO energy values.
HOMO energy of DFPTET, calculated from Eq. (1) was found to be -5.2639 eV and LUMO
energy, calculated using Eq. (2) was found to be -4.0896 eV. The energy gap Eg between

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HOMO and LUMO energy levels was found to be 1.1743 eV from Eq. (3). HOMO and
LUMO energies characterize the electron donating and electron withdrawing ability

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respectively of a group in a molecule. Their energy gap exhibit chemical stability and plays
an important role in identifying molecular electrical transport properties. This assists in

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measuring electron conductivity and other electrochemical properties. On the basis of redox
potentials explicated in the cyclic voltammograms of standard internal reference ferrocene
and DFPTET (Fig. 12), HOMO-LUMO energies and Eg were calculated.

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3
12
2 (b)
10 (a)
8 1
6 0
Current / x 10 A

4
-1
Current / x 10-6 A

-6

2
0 -2
-2 -3
-4
-4
-6
-8 -5
D

-10 -6
-12
-7
-14
-16 -8
0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 1.2 1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6
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Potential / V Potential / V

Fig. 12. Cyclic voltammograms of (a) 2 mM Ferrocene standard and (b) 2 mM DFPTET at
EP

platinum working electrode. Solvent: Acetonitrile + 0.1 M LiClO4. Scan rate: 50 mVs-1.

Table. 6
C

HOMO-LUMO energies of DFPTET by B3LYP/6-31+G(d,p) method and cyclic

voltammetry.
AC

Parameters Theoretical values Cyclic

(B3LYP/6-31+G(d,p)) Voltammetry
EHOMO (eV) -6.0995 -5.2639
ELUMO (eV) -2.0561 -4.0896
(EHOMO – ELUMO) (eV) 4.0394 1.1743

Eox = 0.8839 V; Ered= -0.2904 V

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3.9 Determination of global reactivity descriptors from HOMO and LUMO energy
values
Chemical hardness (η) of a molecule can be estimated using the chemical stability of a
molecule, which can be determined from Eq. (17) as shown below [28].

η = E − E /2 (17)

where, ELUMO and EHOMO are the values of LUMO and HOMO.

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The experimental chemical hardness value of DFPTET in ground state was found to be
0.5872 eV while the theoretical value was determined to be 2.0217 eV. Chemical hardness

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(η) value was utilized to determine chemical softness of the molecule which can be given as

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in Eq. (18).

S = 1/η (18)

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It was evident from Gaussian studies that the occupied and unoccupied molecular orbitals
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are active in electronic transitions. For the molecule in ground state, the theoretical value
was 0.4946 eV while the experimentally determined softness value was found to be 1.7030
eV. Generally, Eg indicate the nature of the molecule with respect to hardness and softness.
M

Large HOMO-LUMO gap suggest that the molecule is hard whereas smaller HOMO-LUMO
gap indicate that the molecule is soft. From the chemical hardness and softness, which is
D

also supported by the smaller energy gap between HOMO and LUMO energy levels, we can
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confirm that the molecule is soft and is susceptible to more polarization as excitation will be
easier.
EP

The quantification of the tendency of DFPTET to attract electrons, which is electronegativity

index (χ) was expressed in terms of orbital energies using Eq. (19) [34].
C

χ = −E − E /2 (19)

AC

Electronegativity index was found to be -0.5871 eV experimentally and 4.0778 eV

theoretically. This also measures the resistance of an atom or ion or a group of atoms in a
molecule for an entering electronic charge.

The chemical potential value for DFPTET in ground state can be deduced from Eq. (20)
which is given as follows.

μ = E + E /2 (20)

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where, ELUMO and EHOMO are the energy values of LUMO and HOMO. The calculated
chemical potential value for DFPTET in ground state was found to be – 4.6768 eV which is
in reasonably good agreement with the theoretical value of -4.0778 eV. Using chemical
hardness and chemical potential values, the electrophilicity index (ω) was determined
[20, 36]. This index was calculated for DFPTET by using Eq.(21) and was found to be
1.1743 which provides a measure electrophilic power of the molecule whereas the

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theoretical value was found to be 4.1124.

AB
ω= = E + E /2 ∗ 2)/ E − E  (21)

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"C

This index measures the energy lowering of a substance due to the electron flow between

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donor and acceptor. The HOMO-LUMO energies reveal electron donating and withdrawing
ability of the molecule. Eg, the energy gap between HOMO and LUMO exhibit the chemical

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stability of the molecule and helps to evaluate molecular electronic properties thereby
measuring electron conductivity.
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Table. 7
Global reactivity descriptors of DFPTET.
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Parameters Theoretical values Cyclic

(B3LYP/6-31+G(d,p)) Voltammetry
D

Electronegativity (χ) (eV) 4.0778 -0.5871

Chemical hardness (η)(eV) 2.0217 0.5872
TE

Softness (S) (eV) 0.4946 1.7030

Chemical potential (µ)(eV) -4.0778 -4.6768
Electrophilicity index (ω) 4.1124 1.1743
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3.10 Fukui functions

C

Electronegativity (χ), chemical hardness (η) and softness (S) are global descriptors of the
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reactivity of a molecular system. However, the Fukui function is a local reactivity parameter,
defined as the derivative of electron density with respect to the change in the number of
electrons with the positions of the nuclei remaining unaltered [37, 38]. Fukui functions are
indices that give information about the tendency of a molecule to lose or gain an electron
thus predicting which atom in the molecule would be more prone to a nucleophilic or
electrophilic attack. When a molecule accepts an electron, the Fukui function is f+k, which is
incidentally called the index of nucleophilic attack. When a molecule has a tendency to lose
an electron, the Fukui function is f-k which is also termed as the index of electrophilic attack.

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However, in order to quantify the Fukui function, in other words, in order to assign each
atom of a molecular system with a numerical value to indicate its probability to serve as a
reactive site, condensed Fukui functions are employed. The condensed Fukui function
corresponding to f+k and f-k are represented as:

f+k = qk(N+1)-qk(N) (22)

f-k = qk(N)-qk(N-1)

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(23)

fok= qkN + 1 − qkN − 1/2 (24)

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Here qk is the electronic population of atom k in the (N) neutral, (N-1) cationic and (N+1)
anionic state. In the case of DFPTET, the electronic population was calculated by Natural

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Population Analysis (NPA). A new descriptor, ∆f(r), was proposed by Morrel et al [39] for
nucleophilicity and electrophilicity. It is defined as:

∆f(r) = [f+k – f-k ]

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If ∆f(r) > 0, then the site is electrophilic and if ∆(f) < 0 then the site is nucleophilic. This is
how the dual descriptor can be used to determine the nature of the reactive site.
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For DFPTET the order of susceptibility to nucleophilic attack is C3>H19>H20>

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H16>C5>N13>C1>H29>H30>H27>C15>H8>H7>N22>C2>C24. While S17>C21>N18

>C12>F11>C25>N26>H9>C6>N23>C4>N14 are arranged in decreasing order of
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susceptibility to electrophilic attack. The Fukui functions (f+k), (f-k) and ∆(f) are tabulated in
Table 8.
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Table 8.
The condensed Fukui functions (GHI ),( GHJ ), GH'  and dual descriptor ∆f(r)
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Atoms Fukui functions

I J
GH GH GH' ∆f(r)
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C1 0.0019 0.2965 0.1492 −0.2946

C2 -0.1996 -0.0979 −0.1486 −0.1017
C3 -0.0612 0.4735 0.2061 −0.5347
C4 0.0008 -0.0848 −0.0420 0.0856
C5 0.0655 0.3757 0.2206 −0.3102
C6 -0.3102 -0.4207 −0.3654 0.1105
H7 0.0028 0.1548 0.0788 −0.1520
H8 -0.0001 0.1698 0.0848 −0.1699
H9 0.0063 -0.1465 −0.0701 0.1528
F10 -0.0269 -0.3016 −0.1642 0.2747
F11 -0.0213 -0.3085 −0.1649 0.2872

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C12 0.0339 -0.4601 −0.2131 0.4940
N13 -0.2210 0.0847 −0.0682 −0.3057
N14 -0.0430 -0.1213 −0.0822 0.0783
C15 -0.1561 0.0181 −0.0690 −0.1742
H16 -0.0070 0.3176 0.1553 −0.3246
S17 -0.0251 -0.9270 −0.4761 0.9019
N18 -0.0060 -0.5035 −0.2547 0.4976
H19 -0.0077 0.3410 0.1666 −0.3487
H20 0.0056 0.3311 0.1683 −0.3255

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C21 -0.0385 -0.8442 −0.4413 0.8057
N22 0.0357 0.1716 0.1036 −0.1359
N23 -0.0829 -0.1773 −0.1301 0.0944

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C24 0.0507 0.1095 0.0801 −0.0588
C25 0.1858 -0.0882 0.0488 0.2740
−0.1459 0.1916

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N26 -0.0501 -0.2417
H27 -0.0134 0.1645 0.0755 −0.1779
H28 -0.0099 0.1495 0.0698 −0.1594
H29 -0.0166 0.1791 0.0812 −0.1957

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H30 0.0029 0.1934 0.09815 −0.1905
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3.11 Thermodynamic properties
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On the basis of vibrational analysis at the B3LYP/6-31+G(d,p) level, thermodynamic

properties such as entropy (S0m) , heat capacity (C0m,p) and enthalpy (H0m) change were
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calculated and are tabulated in Table 9. It is observed that the values increased from 100K to
1000K. This can be attributed to the enhancement of molecular vibrations upon increasing
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the temperature. The correlation between the thermodynamic properties and temperature is
depicted in the graph (Fig.13) and the corresponding fitting equations are provided below.
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The corresponding fitting equations are mentioned below.

S0m = 284.13 -10T4 -7T3 -5T2 + 1.1208T + 4E; (R2 = 0.9984) (26)
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C0m,p = 43.552 - 10T4 - 6T3 + 0.0007T2 + 0.7211T + 6E; (R2 = 0.9863) (27)
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∆H0m = 5.6685 - 10T4 - 7T3 + 0.0003T2 - 0.0594T; (R2 = 0.9899) (28)

Table 9.
Variation of thermodynamic properties with temperature at B3LYP/6-31+G(d,p) level for
DFPTET

Temperature (K) (S0m) (J/molK) C0p,m (J/molK) ∆H0m (kJ/mol)

100.00 394.8691 121.3360 2.0951
200.00 510.4228 204.6018 8.6672
298.15 146.6230 276.4703 16.1897
300.00 612.2824 287.2818 16.2092
400.00 707.9746 361.0457 33.8856

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500.00 797.1106 421.1531 57.3471
600.00 897.7655 468.4155 89.1491
700.00 956.1612 505.6322 115.2733
800.00 1026.8038 535.4223 147.9850
900.00 1092.2959 559.7062 178.5358
1000.00 1153.2150 579.814 201.2234

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Fig. 13. Correlation graph between thermodynamic parameters and temperature

4. Conclusion
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This research work focusses on the synthesis and theoretical DFT studies of a novel 1,2,4
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triazole derivative, DFPTET. The concurrence of the computational studies was

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corroborated with experimental evidences such as IR, Raman, C NMR and 1H NMR
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spectra. The complete vibrational analysis with PED % was done. The fragmentation pattern
of a sample of the molecule was predicted. The hyperpolarizability of DFPTET was found to
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be three times as much as urea and the NLO properties were theoretically estimated. The
ground state energies associated frontier molecular orbitals were studied theoretically and
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experimentally using cyclic voltammetry. The dipole moment was found to be 5.0847 D.
The molecule was also evaluated for its thermodynamic properties. Global reactivity
descriptors were calculated from the cyclic voltammetry results pertaining to HOMO-
LUMO energies and were compared to theoretical data. Local reactivity indices such as
Fukui functions which helped to predict the region of the molecule susceptible to
electrophilic and nucleophilic attack were also discussed. The plausibility of DFPTET
exhibiting biological activity is currently under investigation.

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Acknowledgements
The authors would like to thank Indian Institute of Science (IISc), Bengaluru, India for
performing the computational analysis and NMR spectral analysis. The authors would like to
thank MNCF facility, CeNSE, IISc, Bengaluru, India for FT-IR and Raman analyses.

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Highlights

• A novel Schiff base bearing 1,2,4 triazole scaffold is studied by DFT/B3LYP

calculations.
• Comparison of spectroscopic characterization of optimized structure with the
experimental results.
• Determination of HOMO-LUMO energy gap by cyclic voltammetry.

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• Molecular electrostatic potential map was used to evaluate the reactivity of the
molecule.

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