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PHARMACEUTICAL AND BIOLOGICAL EVALUATIONS

April 2018; Vol. 5 (Issue 2): 27-39.


www.onlinepbe.com ISSN 2394-0859

Research Article DOI: http://dx.doi.org/10.26510/2394-0859.pbe.2018.04

Molecular structure, HOMO, LUMO, MEP, natural bond orbital


analysis of benzo and anthraquinodimethane derivatives
Tahar Abbaz1*, Amel Bendjeddou1, Didier Villemin2
1
Laboratory of Aquatic and Terrestrial Ecosystems, Org. and Bioorg. Chem. Group, University of Mohamed-Cherif
Messaadia, Souk Ahras, 41000, Algeria
2
Laboratory of Molecular and Thio-Organic Chemistry, UMR CNRS 6507, INC3M, FR 3038, Labex EMC3,
Ensicaen and University of Caen, Caen 14050, France

*For correspondence ABSTRACT


Dr. Tahar Abbaz,
Laboratory of Aquatic and Objective: Optimized molecular structures have been investigated by
Terrestrial Ecosystems, Org. DFT/B3LYP method with 6-31G (d,p) basis set. Stability of Benzo and
and Bioorg. Chem. Group, anthraquinodimethane derivatives 1-4, hyperconjugative interactions,
University of Mohamed- charge delocalization and intramolecular hydrogen bond has been
Cherif Messaadia, Souk analyzed by using natural bond orbital (NBO) analysis. Electronic
Ahras, 41000, Algeria. structures were discussed and the relocation of the electron density was
Email: tahar.abbaz@univ- determined. Molecular electrostatic potential (MEP), local density
soukahras.dz
functional descriptors has been studied. Nonlinear optical (NLO)
properties were also investigated. In addition, frontier molecular orbitals
analyses have been performed from the optimized geometries. An
ionization potential (I), electron affinity (A), electrophilicity index (ω),
chemical potential (µ), electronegativity (χ), hardness (η), and softness
(S), have been investigated. All the above calculations are made by the
method mentioned above.
Methods: The most stable optimized geometries obtained from
DFT/B3LYP method with 6-31G(d,p) basis set were investigated for the
study of molecular structures, nonlinear properties, natural bond orbital
(NBO), molecular electrostatic potential (MEP) and frontier molecular
orbital of Benzo and anthraquinodimethane derivatives.
Results: Reactive sites of electrophilic and nucleophilic attacks for the
investigated molecule were predicted using MEP at the B3LYP/6-
31G(d,p). Compound 4 possesses higher electronegativity value than all
compounds so; it is the best electron acceptor; the more reactive sites for
electrophilic attacks are shown in compounds 1 and 4, for nucleophilic
attacks are indicated in compounds 2 and 3 and the more reactive sites in
radical attacks are detected in compounds 2 and 4.
Conclusions: Compound 1 is softest, best electron donor and more
reactive than all compounds. The calculated first order hyperpolarizability
was found much lesser than reported in literature for urea.
Received: 20 January 2018 Keywords: Tetrathiafulvalenes, Density functional theory, Computational
Accepted: 27 February 2018 chemistry, Electronic structure, Quantum chemical calculations

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Abbaz T. et al. Pharmaceutical and Biological Evaluations 2018; Vol. 5 (2): 27-39.

Introduction confirm its NLO response. In addition, the


molecular electrostatic potential (MEP), frontier
The rational design of new organic molecular molecular orbital analysis properties were
materials requires intensive experimental investigated using theoretical calculations. All
investigations in order to elucidate the the calculations done in this work are obtained by
relationship existing between molecular DFT/B3LYP method with 6-31G(d,p) basis set.
structures and solid state properties. In this field,
cation radical salts of tetrathiafulvalene (TTF) Materials and Methods
derivatives are the subject of intense research
activities owing to their unusual and exciting The quantum chemical calculations of benzo and
electric and magnetic properties.1-4 Such anthraquinodimethane derivatives 1-4 have been
behaviour results from the combination of performed using the B3LYP level of theory
specific electrochemical and structural properties supplemented with the standard 6-31G(d,p) basis
associated with the chemical structure of the TTF set, using the Gaussian 09 program. The entire
core. calculations were performed at DFT levels on
personal computer using Gaussian 09W program
Push-pull chromophores, with the electron donor package, invoking gradient geometry
and acceptor separated by π-conjugating linkers optimization.18,19 Initial geometry generated from
(D–π–A), have been investigated for decades.5 standard geometrical parameters was minimized
Nevertheless, they continue to attract growing without any constraint in the potential energy
interest in view of their promising optoelectronic surface at DFT level, adopting the standard 6-
properties, in particular their second-order and 31G(d,p) basis set.
third-order nonlinear optical (NLO) behavior,
and their potential for application as advanced Results and Discussion
functional materials in molecular devices.6-9 We
have prepared several families of new push-pull Molecular geometry
chromophores featuring intense, batho-
The most stable optimized geometry obtained
chromically shifted intra-molecular charge-
from B3LYP/6-31G(d,p) method and the scheme
transfer (CT) bands, high third-order optical
of numbering of atoms of the molecules benzo
nonlinearities, and interesting redox properties.9-
10 and anthraquinodimethane derivatives 1-4 are
shown in Figure 1. Molecular symmetry can be
The density functional theory (DFT) is an used to predict many molecular properties such as
excellent tool to calculate the reasonable infrared, its dipole. The most optimized structural
vibrational frequencies, molecular geometries, parameters (bond length, bond angle and dihedral
linear and nonlinear optical etc. properties.11-12 angles) calculated by B3LYP with 6-31G(d,p)
B3LYP functional has been previously shown to basis set are presented in Tables 1-4.
provide an excellent compromise between
Molecular electrostatic potential
accuracy and computational efficiency of
vibrational spectra for large and medium size MEP is related to the ED and is a very useful
molecule.13-16 descriptor in understanding sites for electrophilic
and nucleophilic reactions as well as hydrogen
The aim of the work is to investigate the
bonding interactions.20,21 The electrostatic
molecular structures and nonlinear properties of
potential V(r) is also well suited for analyzing
Benzo and anthraquinodimethane derivatives 1-4
processes based on the ‘‘recognition’’ of one
described in literature.17 The study has been
molecule by another, as in drug-receptor, and
complemented by natural bond orbital (NBO)
enzyme–substrate interactions, because it is
calculations with an analysis of the electron
through their potentials that the two species first
charge transfer through the intramolecular
‘‘see’’ each other.22,23 To predict reactive sites of
contacts. Compounds have been predicted. The
electrophilic and nucleophilic attacks for the
first hyper-polarizability calculation helps to
investigated molecule, MEP at the B3LYP/6-

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Figure 1: Optimized molecular structure of benzo and anthraquinodimethane derivatives 1-4.


A=Compound 1, B=Compound 2, C=Compound 3, D=Compound 4.

Table 1: Optimized geometric parameters of compound 1.

Bond Length(Å) Bond Angles(°) Dihedral Angles(°)


R(1,3) 1.450 A(2,1,3) 122.204 D(3,1,2,35) 179.999
R(1,36) 1.086 A(2,1,36) 118.763 D(2,1,3,29) 179.997
R(1,2) 1.356 A(3,1,36) 119.032 D(36,1,3,6) 179.996
R(3,29) 1.376 A(1,3,6) 115.592 D(2,4,32,31) 179.998
R(7,8) 1.395 A(8,7,12) 119.362 D(15,9,10,11) 180.000
R(7,12) 1.396 A(8,7,13) 120.456 D(17,18,30,32) 179.995
R(8,9) 1.397 A(12,7,13) 120.181 D(19,31,32,4) 179.993
R(11,12) 1.403 A(7,8,14) 119.466 D(6,5,9,11) 177.859
R(11,27) 1.768 A(7,8,9) 120.409 D(34,5,9,10) 174.260
R(27,29) 1.778 A(9,8,14) 120.123 D(9,5,34,4) 179.697
R(22,26) 1.085 A(8,9,10) 120.409 D(5,6,7,8) 114.513
R(4,5) 1.450 A(10,11,12) 120.228 D(6,7,15,18) 170.857
R(28,29) 1.777 A(10,11,27) 123.300 D(8,7,15,16) 101.546
R(4,32) 1.375 A(12,11,27) 116.47 D(10,9,11,13) 122.550
R(5,6) 1.355 A(11,27,29) 96.600 D(20,19,23,24) 138.512

31G(d,p) optimized geometry was calculated. Figure 2, these molecules have several possible
Potential decreases in the order blue> green> sites for electrophilic and nucleophilic attacks.
yellow> orange> red. Electrophilic regions are
represented by red, nucleophilic by blue and As seen from the Figure 2 that, in all molecules,
green indicates neutral electrostatic potential. To the regions exhibiting the negative electrostatic
predict reactive sites for electrophilic or potential are localized near the conjugated
nucleophilic attack for the investigated molecule, aromatic rings while the regions presenting the
the MEP at the B3LYP/6-31G(d,p) optimized positive potential are localized vicinity of the
geometry was calculated. As can be seen from the aromatic hydrogen atoms.

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Figure 2: Molecular electrostatic potential surface of benzo and anthraquinodimethane


derivatives 1-4.

Table 2: Optimized geometric parameters of compound 2.

Bond Length(Å) Bond Angles(°) Dihedral Angles(°)


R(1,2) 1.392 A(2,1,6) 118.252 D(6,1,2,11) 178.917
R(1,6) 1.406 A(2,1,41) 120.373 D(2,1,6,45) 175.418
R(1,41) 1.509 A(6,1,41) 121.367 D(41,1,6,5) 175.417
R(2,11) 1.082 A(1,2,3) 124.085 D(2,1,41,43) 122.728
R(2,3) 1.408 A(1,2,11) 116.647 D(2,3,4,8) 168.640
R(3,7) 1.477 A(3,2,11) 119.226 D(7,3,4,5) 168.638
R(3,4) 1.431 A(2,3,4) 117.174 D(12,5,6,1) 178.916
R(7,35) 1.381 A(2,3,7) 122.104 D(5,6,45,46) 122.727
R(7,10) 1.450 A(4,3,7) 120.721 D(3,7,10,40) 177.581
R(9,10) 1.350 A(3,4,8) 120.721 D(35,7,10,9) 171.887
R(9,39) 1.084 A(5,4,8) 122.105 D(38,8,9,10) 171.885
R(13,14) 1.395 A(3,7,10) 115.285 D(19,13,14,15) 179.872
R(13,18) 1.397 A(3,7,35) 126.574 D(20,14,15,16) 179.883
R(53,57) 1.086 A(10,7,35) 118.024 D(21,15,16,17) 179.998
R(13,19) 1.085 A(8,9,10) 123.522 D(15,16,17,33) 179.045
Table 3: Optimized geometric parameters of compound 3.

Bond Length (Å) Bond Angles (°) Dihedral Angles (°)


R(1,2) 1.414 A(2,1,6) 118.175 D(6,1,2,11) 179.910
R(1,6) 1.426 A(2,1,41) 122.682 D(41,1,2,3) 179.018
R(1,41) 1.420 A(6,1,41) 119.109 D(2,1,6,39) 176.107
R(2,3) 1.388 A(1,2,3) 123.462 D(2,3,4,8) 166.602
R(2,11) 1.082 A(1,2,11) 116.448 D(7,3,4,5) 166.603
R(3,4) 1.458 A(3,2,11) 120.080 D(3,7,10,48) 176.863
R(3,7) 1.477 A(2,3,4) 117.761 D(35,7,10,9) 170.797
R(13,19) 1.085 A(2,3,7) 122.212 D(4,8,9,47) 176.861
R(7,10) 1.450 A(4,3,7) 120.021 D(19,13,14,15) 179.833
R(7,35) 1.380 A(3,4,5) 117.762 D(20,14,15,16) 179.859
R(9,47) 1.084 A(5,4,8) 122.211 D(21,15,16,17) 179.985
R(13,14) 1.394 A(3,7,10) 115.728 D(15,16,17,33) 178.936
R(13,18) 1.397 A(3,7,35) 125.994 D(16,17,18,34) 179.406
R(14,15) 1.398 A(10,7,35) 118.142 D(16,17,33,35) 176.515
R(17,33) 1.763 A(8,9,10) 123.545 D(29,23,28,27) 179.833

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Table 4: Optimized geometric parameters of compound 4.

Bond Length (Å) Bond Angles (°) Dihedral Angles (°)


R(1,2) 1.395 A(2,1,6) 119.839 D(16,1,2,3) 179.802
R(1,6) 1.393 A(2,1,16) 119.746 D(2,1,6,19) 178.396
R(1,16) 1.086 A(6,1,16) 120.394 D(17,2,3,4) 176.271
R(2,3) 1.401 A(1,2,3) 121.072 D(7,3,4,5) 177.477
R(2,17) 1.085 A(1,2,17) 119.286 D(2,3,7,10) 139.466
R(3,4) 1.420 A(3,2,17) 119.599 D(4,3,7,45) 137.951
R(3,7) 1.482 A(2,3,7) 123.379 D(8,4,5,6) 178.703
R(7,45) 1.362 A(4,3,7) 117.497 D(18,5,6,1) 176.269
R(23,28) 1.396 A(3,7,45) 123.339 D(10,7,45,44) 176.016
R(24,25) 1.397 A(4,8,9) 113.186 D(4,8,9,15) 139.469
R(24,30) 1.084 A(4,8,48) 123.337 D(48,8,9,10) 137.954
R(25,26) 1.395 A(10,9,15) 119.073 D(4,8,48,47) 176.021
R(27,28) 1.400 A(12,11,13) 119.287 D(8,9,10,11) 177.479
R(27,43) 1.769 A(24,23,29) 120.470 D(10,9,15,22) 176.274
R(44,45) 1.788 A(28,23,29) 120.219 D(7,10,11,13) 178.705

Frontier molecular orbitals (FMOs) These parameters of the titled compound were
obtained by using the following equations. By
To explain several types of reaction and for using Koopman’s theorem for closed-shell
predicting the most reactive position in molecules, the chemical hardness of any
conjugated systems, molecular orbitals and their molecule can be calculated by the following
properties such as energy are used.24 The highest relation:
occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO) are the   I  A / 2
most important orbitals in a molecule. The Eigen
values of HOMO and LUMO and their energy The chemical potential of a molecule is
gap reflect the biological activity of the molecule. calculated by:
A molecule having a small frontier orbitals gap is
more polarizable and is generally associated with   I  A / 2
a high chemical reactivity and low kinetic
stability.25-27 HOMO which can be though as the The softness of a molecule is calculated by:
outer orbital containing electrons, tend to give S  1 / 2
these electrons as an electron donor and hence the
ionization potential is directly related to the Electronegativity of the molecule is calculated
energy of the HOMO. On the other hand LUMO by:
can accept electrons and the LUMO energy is
directly related to electron affinity.28,29 Two   ( I  A) / 2
important molecular orbitals were examined for
the compound 1, HOMO and LUMO which are Electrophilic index of the molecule is calculated
given in Figure 3. by:

Global reactivity descriptors    2 / 2


The global chemical reactivity descriptors such as
Where A=-E HOMO is the ionization potential and
hardness (η), chemical potential (µ), softness (S),
I=-E LUMO is the electron affinity of the molecule.
electronegativity (χ) and electrophilicity index
The calculated values such as EHOMO, ELUMO,
(ω) of the titled compounds have been calculated
ΔEgap, A, I, η, µ, S, χ and ω of benzo and
by using its HOMO and LUMO energy values.
anthraquinodimethane derivatives 1-4 calculated

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by B3LYP/6-31G(d,p) method are given in Table (greater) among all the molecules. Thus,
5. compound 1 is found to be more reactive than all
the compounds. Compound 4 possesses higher
electronegativity value (χ=3.061 eV) than all
compounds so; it is the best electron acceptor.
The value of ω for compound 1 (ω=3.240 eV)
indicates that it is the stronger electrophiles than
all compounds. Compound 1 has the smaller
frontier orbital gap so, it is more polarizable and
is associated with a high chemical reactivity, low
kinetic stability and is also termed as soft
molecule.

Local reactivity descriptors

Fukui function is one of the widely used local


density functional descriptors to model chemical
reactivity and selectivity. The Fukui function is a
local reactivity descriptor that indicates the
preferred regions where a chemical species will
change its density when the number of electrons
is modified. Therefore, it indicates the propensity
of the electronic density to deform at a given
Figure 3. HOMO-LUMO structure with the position upon accepting of donating electrons.30
energy level diagram of compound 1. The Fukui function of the system defines the
more reactive regions in a molecule, the reactivity
As presented in Table 5, the compound which
indices are directly concerned with the selectivity
have the lowest energetic gap is the compound 1
of the molecule towards specific chemical events.
(∆Egap=2.589 eV). This lower gap allows it to be
Using Mulliken atomic charges of neutral, cation
the softest molecule. The compound that have the
and anion state of present molecules, Fukui
highest energy gap is the compound 4
functions (f +k; f-k; f 0k) are calculated.31 Fukui
(∆Egap=3.489 eV). The compound that has the
functions are calculated using the following
highest HOMO energy is the compound 1
equations:
(EHOMO=-4.191 eV). This higher energy allows it
to be the best electron donor. The compound that f k  qN  1  qN  ,
has the lowest LUMO energy is the compound 1
(ELUMO=-1.602 eV) which signifies that it can be
the best electron acceptor. The two properties like for nucleophilic attack,

f k  qN   qN  1,


I (potential ionization) and A (affinity) are so
important, the determination of these two
properties allow us to calculate the absolute
electronegativity (χ) and the absolute hardness for electrophilic attack,
(η). These two parameters are related to the one-
electron orbital energies of the HOMO and f k0  qN  1  qN  1 2 ,
LUMO respectively. Compound 1 has lowest
value of the potential ionization (I=4.191 eV), so for radical attack.
that will be the better electron donor. Compound
1 has the largest value of the affinity (A=1.602 Where +, - and 0 signs show nucleophilic,
eV), so it is the better electron acceptor. The electrophilic and radical attack, respectively.
chemical reactivity varies with the structural of Fukui functions for selected atomic sites in benzo
molecules. Chemical hardness (softness) value of and anthraquinodimethane derivatives 1-4 have
compound 1 (η=1.295 eV, S=0.658 eV) is lesser been listed in Tables 6 and 7.

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Table 5: Quantum chemical descriptors of benzo and anthraquinodimethane derivatives 1-4.

Parameters Compound 1 Compound 2 Compound 3 Compound 4


EHOMO(eV) -4.191 -4.289 -4.447 -4.805
ELUMO(eV) -1.602 -1.520 -1.562 -1.316
ΔEgap(eV) 2.589 2.769 2.885 3.489
IE (eV) 4.191 4.289 4.447 4.805
A (eV) 1.602 1.520 1.562 1.316
μ (eV) -2.896 -0.760 -3.004 -3.061
χ (eV) 2.896 0.760 3.004 3.061
ƞ (eV) 1.295 -0.760 1.442 1.745
S (eV) 0.386 -0.658 0.347 0.287
ω (eV) 3.240 -0.380 3.129 2.685
Table 6: Order of the reactive sites on compounds 1 and 2.

Compound 1 Compound 2
Atom 4C 1C 4C 3C Atom 35C 38C 2C 5C
f+ 0.122 0.097 0.033 0.033 f+ 0.203 0.203 0.062 0.062
Atom 18C 19C 11C 12C Atom 7C 8C 3C 4C
f- 0.014 0.014 0.014 0.014 f- 0.174 0.174 0.080 0.080
Atom 4C 3C 18C 19C Atom 18C 24C 25C 17C
f0 0.020 0.020 0.016 0.016 f0 -0.008 -0.008 -0.008 -0.008
Table 7: Order of the reactive sites on compounds 3 and 4.

Compound 3 Compound 4
Atom 38C 35C 5C 2C Atom 4C 1C 7C 8C
f+ 0.202 0.202 0.081 0.081 f+ 0.122 0.097 0.031 0.031
Atom 7C 8C 1C 6C Atom 27C 35C 28C 34C
- -
f 0.168 0.168 0.104 0.104 f 0.011 0.011 0.011 0.011
Atom 4C 3C 18C 24C Atom 27C 35C 28C 34C
f0 -0.007 -0.007 -0.007 -0.007 f0 0.011 0.011 0.011 0.011

From the Tables 6 and7, the parameters of local occupancy from the localized NBO of the
reactivity descriptors show that 4C is the more idealized Lewis structure into an empty non-
reactive site in compounds 1 and 4 and 35C, 38C Lewis orbital. For each donor (i), and acceptor (j),
are the more reactive sites in compounds 2 and 3 the stabilization energy E(2) associated with the
respectively for nucleophilic attacks. The more delocalization i - j is estimated as
reactive sites in radical attacks are 18C, 27C, for
E 2   Eij  qi F i, j   j   i
2
compounds 2, 4 respectively and 4C for the both
compounds 1 and 3. The more reactive sites for
electrophilic attacks are 7C for compounds 2, 3 Natural bond orbital analysis provides an
and 18C, 27C for compounds 1 and 4 efficient method for studying intra and
respectively. intermolecular bonding and interaction among
bonds, and also provides a convenient basis for
Natural bond orbital analysis (NBO)
investigating charge transfer or conjugative
The second order Fock matrix was carried out to interaction in molecular systems.32 Some electron
evaluate the donor–acceptor interactions in the donor orbital, acceptor orbital and the interacting
NBO analysis. The interaction result is a loss of stabilization energy resulted from the second-

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order micro disturbance theory are where q i is the have a great impact on information technology
donor orbital occupancy, are ε i and ε j diagonal and industrial applications. The first static
elements and F(i, j) is the off diagonal NBO Fock hyperpolarizability (β) calculation was
matrix element reported.33-35 The larger the E(2) performed on the optimized geometry at
value, the more intensive is the interaction B3LYP/6-31G(d,p). The first static
between electron donors and electron acceptors, hyperpolarizability (β0) is a third rank tensor that
i.e. the more donating tendency from electron can be described by a 3 × 3 × 3 matrix. The 27
donors to electron acceptors and the greater the components of the 3D matrix can be reduced to
extent of conjugation of the whole system.36 10 components due to the Kleinman symmetry.37
Delocalization of electron density between The components of µ, α, β are defined as the
occupied Lewis-type (bond or lone pair) NBO coefficients in the Taylor series expansion of the
orbitals and formally unoccupied (anti-bond or energy in the external electric field. When the
Rydgberg) non-Lewis NBO orbitals correspond external electric field is weak and homogeneous,
to a stabilizing donor–acceptor interaction. NBO this expansion of the energy in the external
analysis has been performed on the melamine electric field is weak and homogeneous, this
molecule at the DFT/B3LYP/6-31G(d,p) level in expansion becomes:
order to elucidate the delocalization of electron
1 1 1
density within the molecules. The second-order E  E 0   a  E a   ab  E a E b   abc  E a E b E c   abcd  E a E b E c E d  ...
2 6 24
perturbation theory analysis of Fock matrix in
NBO basis of benzo and anthraquinodimethane where, E0 is the energy of the unperturbed
derivatives 1-4 is given in Tables 8-11. molecules, Ea is the field at the origin, µa is
component of the dipole moment and αab, βabc,
The intra molecular interaction for the title γabcd are the polarizability, first
compounds is formed by the orbital overlap hyperpolarizability and second
between: π(C7-C8) and π*(C11-C12) for hyperpolarizability tensors, respectively. Total
compound 1, π(C13-C14) and π*(C15-C16) for static dipole moment (µ0), mean polarizability
compound 2, π(C15-C16) and π*(C17-C18) for (|α0|), anisotropy of polarizability (Δα) and first
compound 3 and π(C23-C24) and π*(C27-C28) hyperpolarizability (β0), using x, y, z components
for compound 4 respectively, which result into are defined as.
intermolecular charge transfer (ICT) causing
stabilization of the system. The intra molecular
hyper conjugative interactions of π(C7-C8) to

μ0  μ x2  μ y2  μ z2  1/ 2

π*(C11-C12) for compound 1, π(C13-C14) to


π*(C15-C16) for compound 2, π(C15-C16) to  0  1 3 α xx  α yy  α zz 
π*(C17-C18) for compound 3 and π(C23-C24) to
π*(C27-C28) for compound 4 lead to highest 
Δα  2 1/ 2 α xx  α yy   α yy  α zz   α zz  α xx   6α xz2  6α xy2  6α yz2
2 2 2

1/ 2

stabilization of 21.16, 20.00, 21.07 and 20.97 kJ


 0  (  xxx   xyy   xzz ) 2  (  yyy   yzz   yxx ) 2  (  zzz   zxx   zyy ) 2
mol-1 respectively. In case of LP (2) S27orbital to
the π*(C11-C12) for compound 1, LP(2) S33
orbital to π*(C17-C18) for compound 2, LP (2)
S33 orbital to π*(C17-C18) for compound 3, Large value of particular component of the
LP(2) S43 orbital to π*(C27-C28) for compound polarizability and hyperpolarizability indicate a
4 respectively, show the stabilization energy of substantial delocalization of charge in these
19.48, 19.68, 19.60 and 19.08 kJ mol-1 directions. The total molecular dipole moment
respectively. (µ), mean polarizability (α0) and anisotropy
polarizability (Δα) and first hyperpolarizability
Nonlinear optical properties (NLO) (βtotal) of benzo and anthraquinodimethane
derivatives 1-4 are computed and are depicted in
Non-linear optical (NLO) materials play a major Table 12.
role in nonlinear optics and in particular they

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Table 8: Second order perturbation theory analysis of Fock matrix on NBO of compound 1.

Donor(i) ED/e Acceptor(j ED/e E(2) Kcal/mol E(j)-E(i) F(i.j)


a.u a.u
π(C7-C8) 1.67808 π*(C11-C12) 0.47705 21.16 0.25 0.068
π(C9-C10) 1.67808 π*(C11-C12) 0.47705 21.16 0.25 0.068
π(C17-C22) 1.67808 π*(C18-C19) 0.47705 21.16 0.25 0.068
π(C20-C21) 1.67808 π*(C18-C19) 0.47705 21.16 0.25 0.068
π(C7-C8) 1.67808 π*(C9-C10) 0.33806 19.98 0.28 0.067
π(C9-C10) 1.67808 π*(C7-C8) 0.33806 19.98 0.28 0.067
π(C17-C22) 1.67808 π*(C20-C21) 0.33806 19.98 0.28 0.067
π(C20-C21) 1.67808 π*(C17-C22) 0.33806 19.98 0.28 0.067
LP (2) S27 1.75911 π*(C11-C12) 0.47705 19.48 0.25 0.066
LP (2) S28 1.75911 π*(C11-C12) 0.47705 19.48 0.25 0.066
LP (2) S30 1.75911 π*(C18-C19) 0.47705 19.48 0.25 0.066
LP (2) S31 1.75911 π*(C18-C19) 0.47705 19.48 0.25 0.066
π(C11-C12) 1.67346 π*(C7-C8) 0.33806 17.78 0.31 0.066
π(C11-C12) 1.67346 π*(C9-C10) 0.33806 17.78 0.31 0.066
π(C18-C19) 1.67346 π*(C17-C22) 0.33806 17.78 0.31 0.066
π(C18-C19) 1.67346 π*(C20-C21) 0.33806 17.78 0.31 0.066
LP (2) S27 1.75911 π*(C3-C29) 0.40607 17.73 0.27 0.065
LP (2) S28 1.75911 π*(C3-C29) 0.40607 17.73 0.27 0.065
LP (2) S30 1.75911 π*(C4-C32) 0.40607 17.73 0.27 0.065
LP (2) S31 1.75911 π*(C4-C32) 0.40607 17.73 0.27 0.065
Table 9: Second order perturbation theory analysis of Fock matrix on NBO of compound 2.

Donor(i) ED/e ED/e Acceptor E(2) E(j)-E(i) F(i.j)


Kcal/mol a.u a.u
π(C13-C14) 1.68011 π*(C15-C16) 0.33565 20.00 0.28 0.067
π(C23-C28) 1.68011 π*(C26-C27) 0.33565 20.00 0.28 0.067
π(C15-C16) 1.68038 π*(C13-C14) 0.33664 19.81 0.28 0.067
π(C26-C27) 1.68038 π*(C23-C28) 0.33664 19.81 0.28 0.067
LP(2) S33 1.76656 π*(C17-C18) 0.47394 19.68 0.25 0.067
LP(2) S37 1.76656 π*(C24-C25) 0.47394 19.68 0.25 0.067
π(C1-C2) 1.67557 π*(C5-C6) 0.33092 19.51 0.29 0.067
π(C5-C6) 1.67557 π*(C1-C2) 0.33092 19.51 0.29 0.067
π(C3-C4) 1.59383 π*(C1-C2) 0.33092 19.29 0.28 0.067
π(C3-C4) 1.59383 π*(C5-C6) 0.33092 19.29 0.28 0.067
π(C1-C2) 1.67557 π*(C3-C4) 0.43377 18.88 0.28 0.067
π(C5-C6) 1.67557 π*(C3-C4) 0.43377 18.88 0.28 0.067
σ(C9-H39) 1.97289 σ*(C7-C10) 0.02432 5.40 1.03 0.067
σ(C10-H40) 1.97289 σ*(C8-C9) 0.02432 5.40 1.03 0.067
σ(S33-C35) 1.97674 σ*(C3-C7) 0.03093 4.86 1.14 0.067
σ(S37-C38) 1.97674 σ*(C4-C8) 0.03093 4.86 1.14 0.067
σ(C7-C35) 1.98151 σ*(C3-C7) 0.03093 4.53 1.24 0.067
σ(C8-C38) 1.98151 σ*(C4-C8) 0.03093 4.53 1.24 0.067
σ(C17-C18) 1.97575 σ*(C16-C17) 0.02205 4.41 1.29 0.067
σ(C24-C25) 1.67393 σ*(C25-C26) 0.02205 4.41 1.29 0.067

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Table 10: Second order perturbation theory analysis of Fock matrix on NBO of compound 3.

Donor(i) ED/e Acceptor(j) ED/e E(2) Kcal/mol E(j)-E(i) F(i.j)


a.u a.u
π(C15-C16) 1.68001 π*(C17-C18) 0.47396 21.07 0.25 0.068
π(C26-C27) 1.68001 π*(C24-C25) 0.47396 21.07 0.25 0.068
π(C13-C14) 1.67940 π*(C17-C18) 0.47396 20.97 0.25 0.068
π(C23-C28) 1.67940 π*(C24-C25) 0.47396 20.97 0.25 0.068
π(C13-C14) 1.67940 π*(C15-C16) 0.33428 20.03 0.28 0.067
π(C23-C28) 1.67940 π*(C26 -C27) 0.33428 20.03 0.28 0.067
π(C15-C16) 1.68001 π*(C13-C14) 0.33490 19.80 0.28 0.067
π(C26-C27) 1.68001 π*(C23-C28) 0.33490 19.80 0.28 0.067
LP (2) S33 1.76441 π*(C17-C18) 0.47396 19.60 0.25 0.066
LP (2) S37 1.76441 π*(C24-C25) 0.47396 19.60 0.25 0.066
LP (2) S34 1.75185 π*(C17-C18) 0.47396 19.29 0.25 0.066
LP (2) S36 1.75185 π*(C24-C25) 0.47396 19.29 0.25 0.066
LP (2) S34 1.75185 π*(C7-C35) 0.37794 18.41 0.27 0.065
LP (2) S36 1.75185 π*(C8-C38) 0.37794 18.41 0.27 0.065
π(C17-C18) 1.67498 π*(C13-C14) 0.33490 17.78 0.31 0.066
π(C24-C25) 1.67498 π*(C23-C28) 0.33490 17.78 0.31 0.066
π(C1-C6) 1.51959 π*(C2-C3) 0.30667 17.64 0.27 0.065
π(C1-C6) 1.51959 π*(C4-C5) 0.30667 17.64 0.27 0.065
π(C17-C18) 1.67498 π*(C15-C16) 0.33428 17.59 0.31 0.066
π(C24-C25) 1.67498 π*(C26-C27) 0.33428 17.59 0.31 0.066
Table 11: Second order perturbation theory analysis of Fock matrix on NBO of compound 4.

Donor(i) ED/e Acceptor(j) ED/e E(2) Kcal/mol E(j)-E(i) F(i.j)


a.u a.u
π(C23-C24) 1.67932 π*(C27-C28) 0.47248 20.97 0.25 0.068
π(C25-C26) 1.67932 π*(C27-C28) 0.47248 20.97 0.25 0.068
π(C33-C38) 1.67932 π*(C34-C35) 0.47248 20.97 0.25 0.068
π(C36-C37) 1.67932 π*(C34-C35) 0.47248 20.97 0.25 0.068
π(C23-C24) 1.67932 π*(C25-C26) 0.33811 19.94 0.28 0.067
π(C25-C26) 1.67932 π*(C23-C24) 0.33811 19.94 0.28 0.067
π(C33-C38) 1.67932 π*(C36-C37) 0.33811 19.94 0.28 0.067
π(C36-C37) 1.67932 π*(C33-C38) 0.33811 19.94 0.28 0.067
LP(2) S43 1.77196 π*(C27-C28) 0.47248 19.08 0.25 0.066
LP(2) S44 1.77196 π*(C27-C28) 0.47248 19.08 0.25 0.066
LP(2) S46 1.77196 π*(C34-C35) 0.47248 19.08 0.25 0.066
LP(2) S47 1.77196 π*(C34-C35) 0.47248 19.08 0.25 0.066
LP(2) S43 1.77196 π*(C7-C45) 0.30275 17.88 0.28 0.065
LP(2) S44 1.77196 π*(C7-C45) 0.30275 17.88 0.28 0.065
LP(2) S46 1.77196 π*(C8-C48) 0.30275 17.88 0.28 0.065
LP(2) S47 1.77196 π*(C8-C48) 0.30275 17.88 0.28 0.065
π(C27-C28) 1.67363 π*(C23-C24) 0.33811 17.86 0.30 0.066
π(C27-C28) 1.67363 π*(C25-C26) 0.33811 17.86 0.30 0.066
π(C34-C35) 1.67363 π*(C33-C38) 0.33811 17.86 0.30 0.066
π(C34-C35) 1.67363 π*(C36-C37) 0.33811 17.86 0.30 0.066

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Abbaz T. et al. Pharmaceutical and Biological Evaluations 2018; Vol. 5 (2): 27-39.

Table 12: The dipole moments µ (D), polarizability α, the average polarizability α (esu), the
anisotropy of the polarizability Δα (esu), and the first hyperpolarizability β (esu) of benzo and
anthraquinodimethane derivatives 1-4 calculated by B3LYP/6-31G(d,p) method.

Parameters Compound 1 Compound 2 Compound 3 Compound 4


βxxx 0.0001 0.0032 0.0022 0.0098
Βyyy 0.0000 9.0086 7.9717 49.1610
Βzzz -0.0010 0.0001 0.0001 0.0135
Βxyy 0.0000 0.0008 -62.3512 -0.0038
Βxxy -0.0001 -53.1625 -62.3512 134.6598
Βxxz 0.0180 -0.0115 -0.0086 -0.0258
Βxzz 0.0000 -0.0014 -0.0012 0.0015
Βyzz 0.0000 9.6934 1.4569 -16.0974
Βyyz 0.0010 0.0004 0.0002 -0.0203
Βxyz 0.0001 0.2353 -10.8202 0.0019
Βtot(esu)x10-33 0.0180 34.4613 54.0172 167.7234
µx 0.0000 0.0001 0.0000 0.0001
µy 0.0000 0.4567 -0.5289 1.7220
µz 0.0003 -0.0001 -0.0001 -0.0003
µtot(D) 0.0003 0.4567 0.5289 1.7220
αxx -114.1058 -151.1828 33.5363 -186.3754
αyy -152.6176 -180.2313 -1.8893 -199.9477
αzz -174.7878 -210.0422 -31.6470 -192.5924
αxy 0.0000 0.0003 0.0001 0.0001
αxz -0.0006 2.4498 1.4899 -0.0006
αyz 0.0000 -0.0002 0.0000 0.0021
α(esu)x10-24 53.1835 51.1515 56.5804 11.7677
∆α(esu)x10-24 7.8818 7.5806 8.3852 1.7440

Since the values of the polarizabilities (∆α) and important key factors in a NLO system. The
the hyperpolarizabilities (βtot) of the GAUSSIAN DFT/6-31G(d,p) calculated first
09 output are obtained in atomic units (a.u.), the hyperpolarizability value (β) of benzo and
calculated values have been converted into anthraquinodimethane derivatives molecules are
electrostatic units (e.s.u.) (for α; 1 a.u=0.1482 x equal to 0.0180 x 10-33, 34.4613 x 10-33, 54.0172
10-24 e.s.u., for β; 1 a.u=8.6393 x 10-33 e.s.u.). The x 10-33 and 167.7234 x 10-33 esu. The first
calculated values of dipole moment (µ) for the hyperpolarizability of title molecules is
title compounds were found to be 0.0003, 0.4567, approximately 0.00, 0.10, 0.16 and 0.48 times
0.5289 and 1.7220 D respectively, which are than those of urea (β of urea is 343.272 x10-33 esu
approximately one times than to the value for obtained by B3LYP/6-31G (d,p) method). The
urea (µ=1.3732 D). Urea is one of the above results show that benzo and
prototypical molecules used in the study of the anthraquinodimethane derivatives 1-4 might have
NLO properties of molecular systems. Therefore, not the NLO applications.
it has been used frequently as a threshold value
for comparative purposes. The calculated values Conclusions
of polarizability are 53.1835 x 10-24, 51.1515 x
10-24, 56.5804 x 10-24 and 11.7677 x 10-24 esu
The results of this work are complemented and
respectively; the values of anisotropy of the
discussed within the scope of quantum chemical
polarizability are 7.8818, 7.5806, 8.3852 and
calculations with DFT calculations. The MEP
1.7440 esu, respectively. The magnitude of the
map shows that the negative potential sites are on
molecular hyperpolarizability (β) is one of

©Pharmaceutical and Biological Evaluations 37


Abbaz T. et al. Pharmaceutical and Biological Evaluations 2018; Vol. 5 (2): 27-39.

conjugated aromatic rings as well as the positive 7. Barlow S, Marder SR. Functional Organic
potential sites are around the aromatic hydrogen Materials: Syntheses, Strategies and
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about the possible reaction regions for the title 393-437.
structures. The value of the energy separation 8. Tykwinski RR, Gubler U, Martin RE,
between the HOMO and LUMO of compound 1 Diederich F, Bosshard C, Günter P.
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Acknowledgements Nielsen MB, Diederich F, Gross M. Redox
Properties of Linear and Cyclic Scaffolds
This work was generously supported by the Based on Di-and Tetraethynylethene. Eur J
(General Directorate for Scientific Research and Org Chem. 2004:2959-72.
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