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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.
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:
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.
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-
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
Table 8: Second order perturbation theory analysis of Fock matrix on NBO of compound 1.
Table 10: Second order perturbation theory analysis of Fock matrix on NBO of compound 3.
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.
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
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
atoms. These sites may provide information Applications. Wiley-VCH, Weinheim; 2007:
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.
is very small 2.589 eV compared to other Structure-Property Relationships in Third-
compounds and this energy gap gives significant Order Nonlinear Optical Chromophores. J
information about the reactivity of studied Phys Chem. 1998;102B:4451-65.
compounds. So we conclude that compound 1 is 9. May JC, Biaggio I, Bures F, Diederich F.
softest, best electron donor and more reactive Extended conjugation and donor-acceptor
than all compounds. The calculated first order substitution to improve the third-order optical
hyperpolarizability was found much lesser than nonlinearity of small molecules. Appl Phys
reported in literature for urea. Lett. 2007;90:251106/1-251106/3.
10. Gisselbrecht JP, Moonen NNP, Boudon C,
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.
Technological Development, DGRS-DT) and 11. Lee SY, Boo BH. Molecular structure and
Algerian Ministry of Scientific Research. vibrational spectra of 9-Fluorenone density
functional theory study. Bull Korean Chem
Funding: No funding sources Soc. 1996;17:760-4.
Conflict of interest: None declared 12. Devlin FJ, Finley JW, Stephens PJ, Frish MJ.
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