Spectrochimica Acta Part A 75 (2010) 1115–1124

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Experimental and theoretical studies on o-, m- and

p-chlorobenzylideneaminoantipyrines
Ran Zhang a,b , Baotong Du b , Gang Sun b , Yuxi Sun b,c,∗
a
Institute for material Chemistry, Binzhou University, Binzhou 256600, PR China
b
School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, PR China
c
Key Laboratory of Education Ministry for Soft Chemistry and Functional Materials, Nanjing University of Science and Technology, Nanjing 210094, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Three antipyrine derivatives of o-, m- and p-chlorobenzylideneaminoantipyrines were characterized by
Received 28 November 2009 spectral techniques and density functional calculations. The optimized configurations are very close to the
Received in revised form XRD values and are used as foundations to investigate the molecular properties. The spectral assignments
18 December 2009
were attempted to ascribe to the vibrational modes of the detailed substructures with the aid of theo-
Accepted 24 December 2009
retical calculations because of the satisfactory consistencies between the experimental and theoretical
spectra for each of the studied compounds. Raman spectral ascriptions represent that the ␲-conjugated
Keywords:
moieties linked by Schiff base imines are responsible for the excellent Raman scattering activities of these
Chlorobenzylideneaminoantipyrines
Vibrational frequencies
compounds. The linear polarizabilities and first hyperpolarizabilities of the studied molecules indicate
Thermodynamic functions that the compounds are good candidates of nonlinear optical materials. The statistical thermodynamic
Nonlinear optics functions and their correlations with temperatures obtained from the theoretical vibrations are similar
to each other among the isomers.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction opment of the traditionally experimental chemistry [23]. Currently,

Antipyrine and its derivatives have been widely used as phar-
maceuticals due to broad bioactivities as antitumor [1–3], antimi-
crobial [4–6], antiviral [7,8], and analgesic [9], etc. Nowadays,
antipyrine derivatives (APDs) have been accepted as important
biomodel compounds in the biological and medical fields [10]. In
recent years, ADPs have exhibited attractive multi-functional prop-
erties as coordinate [11], antioxidant [12] antiputrefactive [13] and
optical [14,15] characteristics in chemical and material fields. It
is well known that the macromolecules containing macroscopic
␲-electron systems have attractive opto-related properties such
as nonlinear optics (NLO) [16–19], fluorescence [20,21] and pho-
toelectricities [22], etc., wherein the NLO of materials is at the
forefront of current research due to its importance in technical
fields of telecommunications, signal processing, and optical inter-
connections etc. These points prompt us to further investigate on
the APDs bridged aromatic rings through Schiff base imines in quest
to explore new functional materials in our work.
With the development of computer techniques and computa-
tional chemistry, the quantum chemistry presents insights into
electronic structures of molecules and strongly propels the devel-
density functional theory (DFT) method has been accepted as a
popular post-HF approach for the computation of structural char-
acteristics, vibrational frequencies and energies of molecules by the
ab initio community [24] and for the efficiency and accuracy with
respect to the evaluation of a number of molecular properties [25].
A suitable quantum chemical study is helpful to insightfully clar-
ify experimental phenomena and to economically predict material
properties.
Considering the above-mentioned aspects and as an exten-
sion of our work [26–33], our group is going on to investigate
on APDs by experimental techniques and theoretical methods. In
this work, the vibrational spectral, thermodynamic and nonlinear
optical properties were investigated on three monochlorine-
substituted benzylideneaminoantipyrines, viz., o-chlorobenzyl-
ideneaminoantipyrine (o-CBIAAP), m-chlorobenzylideneamino-
antipyrine (m-CBIAAP) and p-chlorobenzylideneaminoantipyrine
(p-CBIAAP). The experimental measurements and theoretical sim-
ulations presented significant photosensitive properties, especially
of nonlinear optics. Herein, the detailed research results were
reported for these isomers in this work.
2. Experimental and theoretical methods

∗ Corresponding author at: School of Chemistry and Chemical Engineering, Qufu 2.1. Experimental
Normal University, Qufu 273165, PR China. Tel.: +86 537 4456301;
fax: +86 537 4456305. The FT-IR spectra of the solid compounds were recorded in
E-mail address: yuxisun@163.com (Y. Sun). the region of 3500–400 cm−1 in evacuation mode with a scanning

1386-1425/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2009.12.067
1116 R. Zhang et al. / Spectrochimica Acta Part A 75 (2010) 1115–1124
speed of 30 cm−1 min−1 and a spectral width of 2.0 cm−1 on Bruker
IFS 66V spectrophotometer using KBr pellet. The Raman spectra
of the solid samples were measured in the region 3500–100 cm−1
with a spectral resolution of 1.0 cm−1 in the backscattering config-
uration on a RENISHAW inVia Raman microscope with a counter
current detector and a 785 nm diode laser excitation.
All chemicals (reagent grade) were purchased from commercial
sources and used without further purification. The title com-
pounds were respectively synthesized according to the classical
condensation of aldehyde with ammonia [34] and the prepa-
ration technique was explained in previous studies [26–30,35].
The preparations of o-, m- and p-CBIAAPs were prepared by the
respective condensation of 2-, 3-, or 4-chlorobenzaldehydes and
4-aminoantipyrine with 1:1 stoichiometric ratio in MeOH sol-
vent with stirring for 1 h at room temperature to give yellow
precipitates, which were collected by filtration and were recrys-
tallized from MeOH. The yields of the compounds are all beyond
90%.
2.2. Theoretical
In this work, the quantum chemical study was used to make
definite assignments for the fundamental normal modes, and to
clarify the experimental FT-IR and FT-Raman spectral bands, and
to give additional thermodynamic functions and nonlinear optical
properties for the title compounds.
For meeting the requirements of accuracy and economy, the
theoretical method and basis set should be considered firstly. The
density functional theory (DFT) has been proved to be extremely
useful in treating molecular electron relativities, and the basis set
of 6-31G(d) has been used as a very effective and economical level
for fairly large organic molecules [36]. Basing on the points, the
density functional Becke3-Lee-Yang-Parr (DFT/B3LYP) with stan-
dard 6-31G(d) basis set was adopted to compute the properties of
the studied compounds in this work. All the calculations were per-
formed using Gaussian 03W program package [37] with the default
convergence criteria.
For each of the investigated molecules, the initial geometrical
configuration was generated from its X-ray diffraction (XRD) crys-
tallographic data, and the optimized geometry corresponding to the
minimum on the potential energy surface was obtained by solving
self-consistent field equation iteratively without any constraints.
The harmonic vibrational frequencies were analytically calculated
by taking the second-order derivative of energy using the same
level of theory. Normal coordinate analysis was performed to obtain
full description of the molecular motion pertaining to the normal
modes using the GaussView program [38]. Simultaneously, the sta-
tistical thermodynamic functions were theoretically predicted by
the harmonic frequencies of the optimized structures for each of
the title compounds.
The Raman scattering activities (Si ) calculated by Gaussian 03W
program were suitably converted to relative Raman intensities (Ii )
using the following relationship derived from the basic theory of
Raman scattering stated in previous Refs. [39,40]:
f (v0 − vi )4 Si
Ii =
vi [1 − exp(−hc vi /kT )]
where v0 is the exciting frequency (in cm−1 units), vi is the vibra-
tional wavenumber of the ith normal mode, h, c and k are universal
constants, and f is the suitably chosen common scaling factor for all
the peak intensities.
The molecular properties related to the nonlinear optics (NLO)
can be obtained by the following methods stated previously
[41–51].
For a molecule, the correlation of the molecular polarization p
and its external field F is as follows:
p = 0 + ˛ij Ej + ˇijk Ej Ek + ijkl Ej Ek El + · · · (2)
where 0 is the molecular dipole moment, ˛ij is the linear polar-
izability, ˇijk is the first-order hyperpolarizability and  ijkl is the
second-order hyperpolarizability, in which each of the i, j, k and l
denotes either of the x, y and z axes determined arbitrarily.
These tensors are defined as coefficients of the Buckingham type
expansion of the total energy with respect to the applied field F(=
F x , F y , F z ).
 1 1
E = E0 − i F i − ˛ij F i F j − ˇijk F i F j F k
2 6
i ij ijk
1 
− ijkl F i F j F k F l + · · · (3)
24
ijkl
where E0 is the energy of the unperturbed molecule, Fi is the field at
the origin, i , ˛ij and ˇijk are the components of the dipole moment,
polarizability and first-order hyperpolarizability, respectively.
The total static dipole moment (0 ), polarizability (˛0 ) and first-
order hyperpolarizability (ˇ0 ) using the x, y, z components are
defined as:

0 = 2x + 2y + 2z (4)
˛xx + ˛yy + ˛zz
˛0 = (5)
3

ˇ0 =
2 2
(ˇxxx + ˇxyy + ˇxzz ) + (ˇyyy + ˇxxy + ˇyzz ) + (ˇzzz + ˇxxz + ˇyyz )
2
(6)
3. Results and discussion
The schematic diagram with atomic numbering for the title
compounds is given in Scheme 1 for clarity and expression in the
text.
3.1. Optimized structures
The first task for the computational work is to determine the
optimized geometries of the studied molecules. The calculated
structural parameters containing bond lengths and angles using
B3LYP method with 6-31G(d) basis set are listed in Table 1 along
with the available XRD data for o-CBIAAP [27], m-CBIAAP [28] and
p-CBIAAP [27].
As shown in Table 1, most of the optimized bond lengths
are slightly longer than the experimental values agreeing within
0.038 Å and the bond angles are slightly different from the exper-
imental ones agreeing within 5.8◦ . The structural discrepancy is
due to the fact one isolated molecule considered in theoretical
calculations contrary to packing molecules with intermolecular
interactions recorded in condensed phase in the XRD measure-
ments.
The same structural characteristics as experimental explana-
tions can be also observed in the theoretical calculations, such
as, the distances of C8–N3 and N3–C12 show single–double and
imine double bond characteristics, respectively, and the bigger pi-
(1)
conjugated moieties have been formed by the pyrazole and No. 3
phenyl rings bridged through Schiff base imines. As important geo-
metrical characteristics for the compounds, the absolute errors of
the theoretical bond distances of C O and C N are −0.005 Å and
+0.013 Å in o-CBIAAP, −0.003 Å and +0.009 Å in m-CBIAAP, −0.005 Å
and +0.014 Å in p-CBIAAP, respectively.
Although the theoretical configurations are not exactly close
to the XRD values for the studied compounds, they are gener-
ally accepted that bond lengths and bond angles depend upon
 R. Zhang et al. / Spectrochimica Acta Part A 75 (2010) 1115–1124
Scheme 1. The schematic diagrams with atomic numbering for the title compounds.
the method and the basis set used in the calculations. The opti-
mized geometrics represent good approximations and can be used
as foundations to calculate molecular parameters to clarify exper-
imental phenomena and to further predict other properties.
3.2. Vibrational spectra
It is well known that the harmonic frequencies by DFT calcu-
lations are usually higher than the corresponding experimental
ones due to the facts of the electron correlation approximate treat-
ment, anharmonicity effects and basis set deficiencies, etc. [52,53].
After scaling, the theoretical frequencies will match well with
experimental ones. Based on the point, the theoretical harmonic
frequencies were scaled by the empirical factor of 0.9614 according
to Ref. [54] to correct the theoretical errors in this work.
The experimental FT-IR and FT-Raman spectra for the title com-
pounds are respectively shown in Fig. 1 and Fig. 2, where the
infrared and Raman intensities are plotted against the vibrational
wavenumbers. For comparison, the theoretical IR and Raman spec-
tra were simulated by using pure Lorentizian band shapes with a
bandwidth of 10 cm−1 and respectively inserted in Figs. 1 and 2
along with the corresponding experimental spectra.
For comparison, the experimentally observed absorption
wavenumbers of the title compounds with the theoretically simu-
lated data including harmonic frequencies, proposed assignments
and vibrational intensities were summarized in Table 2. All the
present molecules belong to C1 point group with 39 atoms and
111 normal vibrational modes. The mode numbers were extracted
from the output results of the theoretical calculations of the investi-
gated molecules, and selected modes were numbered from small to
big frequency, and the corresponding proposed vibrational assign-
ments were made on the basis of the relative intensities, magnitude
of the frequencies and the normal coordinate analysis with the aid
of the GaussView program [38] and were also listed in the last col-
umn in Table 2. As seen from Table 2, the discrepancies between
the calculated and experimental values were mostly smaller than
30 cm−1 except the significant error appeared by C O stretching
mode.
On the whole, the infrared features are more complicated than
the Raman spectra for each of the studied compounds; and the
infrared or Raman spectra of the isomers are very similar to
each other, which results in that these compounds are difficultly
distinguished from their spectral features without theoretical cal-
culations. As seen from Figs. 1, 2 and Table 2, the theoretically
predicated vibrational frequencies are in good agreement with
the experimental wavenumbers, thus, the features can be dis-
tinguished by some slightly spectral discrepancies with the aid
of theoretical calculations. Owing to the fact that the detailed
spectral assignments have been given in Table 2 and the spectra
with vibrational intensities have been illustrated in Figs. 1 and 2,
we mainly discuss vibrational characteristic peaks and give some
1117
interpretations for these experimental and theoretical spectra
below.
The bands observed at 1648, 1643 and 1653 cm−1 are ascribed
to the C O stretching modes in the FT-IR spectra of o-, m- and
p-CBIAAPs, respectively, while the theoretically calculated values
of about 1700 cm−1 wavenumbers show positive deviations. The
errors are due to the facts that the calculated C O bond distances
are shorter than experimental values stated above and the stretch-
ing vibrational modes are easily infected with the intra/inter-
molecular hydrogen bonds [55,56] in these molecular packing
structures [27,28]. The similar phenomena have been also found
in the dichloro-substituted benzylideneaminoantipyrines [32,33].
The identification of the pyrazole ring vibrations is a very dif-
ficult task because of the mixing modes with several bands and
methyl, ketone, imine, phenyl substituted effects. Fortunately, the
B3LYP calculated wavenumbers show excellent agreements with
the corresponding experimental values, which is very helpful for
us to assign the vibrational spectral peaks. The bands observed at
414, 456, 723 cm−1 in o-CBIAAP, 443, 586, 736 cm−1 in m-CBIAAP
and 419, 441, 716 cm−1 in p-CBIAAP are ascribed to the pyra-
zole ring puckering vibrations mixed partly with other vibrational
modes. The peaks observed at 566 cm−1 in o-CBIAAP, 555 cm−1 in
m-CBIAAP and 589 cm−1 in p-CBIAAP are ascribed to the C7–C8–C9
angle bending mixed partly No. 3 phenyl ring vibrations. The
wavenumbers observed at about 623 cm−1 are mixing modes of
C7–N1–N2 and No. 1 phenyl ring angle bending. The peaks observed
at 1304 cm−1 in o-CBIAAP, 1305 cm−1 in m-CBIAAP and 1277 cm−1
in p-CBIAAP are designated to the C7–N1, C8–N3 and phenyl C–H
in-plane wagging modes. More detailed assignments can be seen
in Table 2.
The bands observed at about 500 and 685 cm−1 are designated
to the phenyl puckering modes. The bands observed at about 550,
600 and 620 cm−1 in the FT-IR spectra are ascribed to the benzene
ring angle bending modes. The theoretically computed values of the
angle bending modes show good agreements with the experimen-
tal ones. The C–H out-of-plane and in-plane wagging for benzene
rings are in the bands of 666–953 cm−1 with medium intensities
and 1023–1461 cm−1 with weak intensities along with the cor-
responding skeleton deformations. Apparently, the benzene ring
puckering and angle bending vibrations are described as mixed
modes partially with C–H out-of-plane and in-plane waging vibra-
tions, respectively. In FT-IR spectra of the compounds, the breathing
vibrations of benzene rings in each of the isomers respectively
appear one band at 1022 cm−1 in o-CBIAAP, 1018 cm−1 in m-CBIAAP
and 1004 cm−1 in p-CBIAAP. While in the FT-Raman spectra, the
breathing modes exhibit one weak peak at 995 cm−1 in o-CBIAAP,
one medium peak at 997 cm−1 in m-CBIAAP and two weak peaks
at 993 and 1007 cm−1 in p-CBIAAP. The medium/strong peaks
observed in the infrared spectra of the studied compounds in the
band of 1554–1608 cm−1 are mainly ascribed to the C C stretching
modes.
1118 R. Zhang et al. / Spectrochimica Acta Part A 75 (2010) 1115–1124

Table 1
Selected geometric parameters for the title compounds.a .

o-CBAP m-CBAP p-CBAP

Exp. Theo. Exp. Theo. Exp. Theo.

Bond lengths (Å)

C1–C2 1.380 (3) 1.401 C1–C2 1.366 (4) 1.401 C1–C2 1.385 (3) 1.401
C2–C3 1.376 (3) 1.394 C2–C3 1.375 (4) 1.394 C2–C3 1.380 (3) 1.394
C3–C4 1.374 (4) 1.397 C3–C4 1.360 (7) 1.397 C3–C4 1.369 (5) 1.397
C4–C5 1.374 (4) 1.395 C4–C5 1.361 (6) 1.395 C4–C5 1.369 (3) 1.395
C5–C6 1.379 (3) 1.395 C5–C6 1.387 (5) 1.395 C5–C6 1.382 (3) 1.395
C1–C6 1.382 (3) 1.401 C1–C6 1.377 (4) 1.401 C1–C6 1.382 (3) 1.401
N1–C1 1.421 (3) 1.421 N1–C1 1.428 (3) 1.421 N1–C1 1.420 (2) 1.421
N1–N2 1.398 (3) 1.414 N1–N2 1.400 (3) 1.414 N1–N2 1.406 (2) 1.414
N1–C7 1.401 (3) 1.418 N1–C7 1.396 (3) 1.417 N1–C7 1.405 (2) 1.417
C7–C8 1.434 (3) 1.469 C7–C8 1.438 (3) 1.468 C7–C8 1.431 (2) 1.469
C8–C9 1.372 (3) 1.372 C8–C9 1.365 (3) 1.372 C8–C9 1.369 (2) 1.372
N2–C9 1.355 (3) 1.386 N2–C9 1.362 (3) 1.386 N2–C9 1.353 (2) 1.386
O1–C7 1.230 (2) 1.225 O1–C7 1.229 (3) 1.226 O1–C7 1.231 (2) 1.226
C9–C10 1.480 (3) 1.491 C9–C10 1.477 (4) 1.491 C9–C10 1.482 (3) 1.491
N2–C11 1.455 (3) 1.469 N2–C11 1.460 (4) 1.468 N2–C11 1.459 (3) 1.469
N3–C8 1.392 (2) 1.382 N3–C8 1.395 (3) 1.382 N3–C8 1.392 (2) 1.383
N3–C12 1.278 (3) 1.291 N3–C12 1.280 (3) 1.289 N3–C12 1.276 (2) 1.290
C12–C13 1.465 (3) 1.470 C12–C13 1.459 (3) 1.468 C12–C13 1.462 (3) 1.466
C13–C14 1.381 (3) 1.408 C13–C14 1.395 (4) 1.404 C13–C14 1.386 (3) 1.404
C14–C15 1.388 (4) 1.395 C14–C15 1.377 (4) 1.394 C14–C15 1.377 (3) 1.393
C15–C16 1.358 (4) 1.393 C15–C16 1.367 (5) 1.395 C15–C16 1.367 (3) 1.394
C16–C17 1.371 (5) 1.399 C16–C17 1.379 (4) 1.387 C16–C17 1.373 (3) 1.398
C17–C18 1.374 (3) 1.388 C17–C18 1.375 (4) 1.398 C17–C18 1.378 (3) 1.389
C13–C18 1.393 (3) 1.409 C13–C18 1.382 (4) 1.406 C13–C18 1.383 (3) 1.407
Cl1–C14 1.742 (3) 1.763 Cl1–C17 1.741 (3) 1.763 Cl1–C16 1.743 (2) 1.759

Bond angles (◦ )
C2–C1–C6 120.4 (2) 120.1 C2–C1–C6 120.6 (2) 120.1 C2–C1–C6 120.1 (2) 120.1
C1–C2–C3 119.6 (2) 119.4 C1–C2–C3 119.7 (3) 119.4 C1–C2–C3 119.2 (2) 119.4
C2–C3–C4 120.3 (2) 120.8 C2–C3–C4 120.5 (3) 120.7 C2–C3–C4 120.9 (2) 120.8
C3–C4–C5 120.0 (2) 119.5 C3–C4–C5 120.0 (4) 119.5 C3–C4–C5 119.7 (2) 119.5
C4–C5–C6 120.4 (2) 120.5 C4–C5–C6 120.6 (4) 120.5 C4–C5–C6 120.6 (2) 120.5
C1–C6–C5 119.3 (2) 119.7 C1–C6–C5 118.6 (3) 119.7 C1–C6–C5 119.4 (2) 119.7
N2–N1–C1 119.1 (2) 119.0 N2–N1–C1 120.1 (2) 119.1 N2–N1–C1 119.1 (1) 119.1
N2–N1–C7 109.3 (2) 109.8 N2–N1–C7 109.0 (2) 109.8 N2–N1–C7 108.6 (1) 109.8
C1–N1–C7 122.1 (2) 123.8 C1–N1–C7 122.1 (2) 123.9 C1–N1–C7 122.4 (1) 123.9
N1–N2–C9 107.4 (2) 106.6 N1–N2–C9 107.6 (2) 106.6 N1–N2–C9 107.3 (1) 106.6
N1–N2–C11 118.0 (2) 114.2 N1–N2–C11 118.2 (2) 114.3 N1–N2–C11 117.1 (2) 114.2
C9–N2–C11 125.1 (2) 119.3 C9–N2–C11 124.9 (2) 119.4 C9–N2–C11 124.8 (1) 119.3
N1–C1–C2 118.2 (2) 118.8 N1–C1–C2 118.4 (2) 118.8 N1–C1–C2 118.1 (2) 118.8
N1–C1–C6 121.4 (2) 121.1 N1–C1–C6 120.9 (2) 121.1 N1–C1–C6 121.8 (2) 121.1
O1–C7–N1 123.6 (2) 124.4 O1–C7–N1 123.0 (2) 124.4 O1–C7–N1 122.9 (2) 124.4
O1–C7–C8 131.6 (2) 130.9 O1–C7–C8 132.0 (2) 131.0 O1–C7–C8 131.8 (2) 130.9
N1–C7–C8 104.7 (2) 104.6 N1–C7–C8 105.0 (2) 104.6 N1–C7–C8 105.3 (1) 104.6
N3–C8–C7 129.4 (2) 129.1 N3–C8–C7 128.7 (2) 129.0 N3–C8–C7 129.3 (1) 129.1
N3–C8–C9 122.1 (2) 123.1 N3–C8–C9 122.8 (2) 123.2 N3–C8–C9 122.4 (2) 123.2
C7–C8–C9 108.1 (2) 107.7 C7–C8–C9 108.3 (2) 107.8 C7–C8–C9 107.9 (2) 107.7
N2–C9–C8 110.0 (2) 110.9 N2–C9–C8 109.6 (2) 110.8 N2–C9–C8 110.4 (1) 110.8
N2–C9–C10 121.7 (2) 121.6 N2–C9–C10 121.2 (2) 121.6 N2–C9–C10 121.9 (2) 121.6
C8–C9–C10 128.3 (2) 127.6 C8–C9–C10 129.2 (2) 127.6 C8–C9–C10 127.8 (2) 127.5
C8–N3–C12 119.9 (2) 120.8 C8–N3–C12 119.9 (2) 120.9 C8–N3–C12 120.4 (2) 120.7
N3–C12–C13 120.5 (2) 120.3 N3–C12–C13 122.1 (2) 121.4 N3–C12–C13 121.6 (2) 121.5
C12–C13–C14 122.8 (2) 122.5 C12–C13–C14 119.8 (2) 119.3 C12–C13–C14 119.6 (2) 119.2
C12–C13–C18 121.0 (2) 120.5 C12–C13–C18 121.4 (2) 121.4 C12–C13–C18 122.2 (2) 122.1
C14–C13–C18 116.2 (2) 117.1 C14–C13–C18 118.8 (2) 119.3 C14–C13–C18 118.3 (2) 118.6
C13–C14–C15 122.7 (2) 121.7 C13–C14–C15 120.8 (3) 120.5 C13–C14–C15 121.5 (2) 121.2
C14–C15–C16 119.2 (3) 119.7 C14–C15–C16 119.9 (3) 120.4 C14–C15–C16 118.5 (2) 118.9
C15–C16–C17 120.1 (2) 119.9 C15–C16–C17 119.7 (3) 118.7 C15–C16–C17 121.7 (2) 121.2
C16–C17–C18 120.4 (3) 119.8 C16–C17–C18 121.1 (3) 121.7 C16–C17–C18 119.1 (2) 119.2
C13–C18–C17 121.5 (3) 121.8 C13–C18–C17 119.7 (2) 119.4 C13–C18–C17 120.8 (2) 120.9
Cl1–C14–C13 119.8 (2) 121.0 Cl1–C17–C16 119.9 (2) 119.0 Cl1–C16–C15 119.0 (2) 119.4
Cl1–C14–C15 117.6 (2) 117.2 Cl1–C17–C18 119.0 (2) 119.3 Cl1–C16–C17 119.3 (2) 119.3
a
Experimental data from Refs. [26,27] for the title compounds.

The imine C–H out-of-plane bending vibrational modes display
weak peaks at 971, 962 and 967 cm−1 in FT-IR spectra of o-, m-
and p-CBIAAPs, respectively. The corresponding calculated modes
have been found to be consistent with the recorded spectral val-
ues. The imine C–H in-plane bending modes computed at about
1373 cm−1 are in excellent agreement with experimental assign-
ments at 1379,1374 and 1375 cm−1 in the FT-IR spectra of o-, m-
and p-CBIAAPs, respectively. The wavenumbers at about 1560 cm−1
(observed)/1572 cm−1 (found) in the Raman spectra are ascribed to
the stretching modes of double bonds of the conjugated moieties
among the atoms of C9/C8/N3/C12/C13/C14/C15/C16/C17/C18. In
Raman spectra, the peaks at 1588 cm−1 (observed)/1600 cm−1
(found) in o-CBIAAP, 1592 cm−1 (observed)/1607 cm−1 (found)
in m-CBIAAP and 1609 cm−1 (observed)/1608 cm−1 (found) in p-
 R. Zhang et al. / Spectrochimica Acta Part A 75 (2010) 1115–1124 1119

Table 2
Comparison of selected experimental and theoretical spectra (IR and Raman) of the title compounds.a .

Modes Experimental Theoretical Approximate assignments

IR Raman Freq. IIR IRaman

o-CBAP
24 414 414 24.1 2.5 ␯R2,3
25 456 442 10.9 0.3 ␯R2
27 471 462 7.2 1.4 ␯R3
28 502 498 7.3 0.3 ␯R1
30 566 553 49.3 1.5 ␣C7C8C9 + ␣R3
31 592 574 18.0 2.8 ␯R2
34 621 623 35.1 1.0 ␣R1 + ␣C7N1N2
35 667 657 15.5 0.6 ␣R3
36 677 665 11.6 0.1 ␶R2
37 690 683 25.8 0.1 ␯R1 + ␥CH of R1
40 723 723 12.2 0.1 ␥CH of R1,3 + ␯R2
41 757 745 64.3 0.3 ␥CH of R1,3
44 832 831 817 5.1 1.6 ␥CH of R1
46 874 876 855 3.4 0.1 ␤imine
48 929 913 11.3 6.0 C7C8 + C9N2 + ␳CH3
52 949 954 0.2 0.0 ␥CH of R3
53 995 978 0.1 7.4 ␪R1
54 971 981 8.8 0.7 ␥CH of imine
56 1022 1014 47.3 1.0 ␪R3
58 1039 1030 1030 19.5 3.6 ␳CH3
61 1071 1064 12.0 3.4 ␤CH of R1 + C7N1
63 1112 1121 1103 26.3 1.5 ␤CH of R3 + C-Cl
64 1128 1122 120.7 1.0 ␳CH3
65 1161 1137 34.4 12.8 ␳CH3 + C7N1 + C8N3
70 1208 1212 1195 9.3 44.6 C12C13 + ␤CH of R3
71 1268 1254 35.4 0.1 ␤CH of R3
72 1284 1272 1274 187.8 4.8 C1N1 + C8N3 + ␤CH of R1,3
73 1304 1289 71.6 0.5 C C of R1,3 + C1N1 + ␤CH of R1,3
76 1334 1314 1316 39.3 2.4 C7N1 + C9N2 + C8N3 + ␤CH of R1
77 1362 1366 1362 23.9 1.3 ␤CH of CH3 +␤CH of imine
78 1379 1375 101.3 3.4 ␤CH of imine
79 1416 1414 1397 97.5 3.7 C7C8 + N2C9 + C9C10 + ␤CH of CH3
80 1429 1435 1422 20.2 9.3 ␤CH of CH3
84 1455 1454 17.5 1.0 ␦CH3
85 1471 1458 11.0 1.7 ␦CH3 + ␤CH of R1
88 1487 1485 75.2 0.5 ␦CH3 + ␤CH of R1
90 1565 1560 1571 30.8 99.0 C8C9 + N3C12 + C C of R3
92 1590 1591 148.7 6.7 C C of R1,3 + C8C9 + N3C12
94 1588 1600 13.6 51.6 N3C12 + C C of R3
95 1650 1654 1704 211.7 1.4 C O
96 2933 2926 47.4 0.5 CH of CH3
107 3067 3086 37.2 0.9 CH of R1,3
m-CBAP
26 443 439 12.9 0.1 ␯R2
27 443 445 12.3 1.4 ␯R3
28 500 496 6.9 0.3 ␯R1
29 555 544 31.5 0.3 ␣C7C8C9 + ␣R3
31 586 576 18.5 2.8 ␯R2
34 623 623 35.8 1.0 ␣R1 + ␣C7N1N2
36 673 669 23.2 0.1 ␶R2 + ␯R3 + ␥CH of R3
37 682 672 9.0 0.1 ␯R3 + ␥CH of R3
38 702 685 42.3 0.1 ␯R1 + ␥CH of R1
39 712 699 22.3 0.2 ␣R1,3 + ␣N3C12C13
40 736 720 12.6 0.1 ␥CH of R1 + ␯R2
41 757 746 41.9 0.3 ␥CH of R1
42 780 767 24.9 0.1 ␥CH of R3
44 838 855 832 12.2 1.6 ␣R1 + C1N1 + C9N2 + C9C10
48 855 917 893 14.0 6.0 ␤imine
49 885 913 9.1 0.8 C7C8 + C9N2 + ␳CH3
53 997 975 4.4 7.4 ␪R3
54 993 978 10.8 0.7 ␥CH of imine
56 1018 1006 14.6 1.0 ␪R1 + N1N2
58 1039 1031 16.9 3.6 ␳CH3
61 1068 1064 22.1 3.4 ␤CH of R1
64 1128 1122 135.0 1.0 ␳CH3
65 1157 1136 53.7 12.8 ␳CH3 + C7N1 + C8N3
70 1210 1121 1195 51.2 44.6 C12C13 + ␤CH of R3
72 1305 1313 1279 239.6 4.8 C1N1 + C8N3 + ␤CH of R1,3
76 1342 1342 1317 37.0 2.4 C C of R1 + C7N1 + ␤CH of R1
78 1373 1367 1371 92.3 3.4 C9N2 + ␤CH of imine
79 1408, 1426 1398 115.3 3.7 C7C8 + N2C9 + C9C11 + ␤CH of CH3
80 1424 1417 13.6 9.3 ␤CH of R3
1120 R. Zhang et al. / Spectrochimica Acta Part A 75 (2010) 1115–1124

Table 2 (Continued )

Modes Experimental Theoretical Approximate assignments

IR Raman Freq. IIR IRaman

81 1453 1422 19.0 3.5 ␤CH of CH3

86 1484 1466 32.7 0.4 ␦CH3
88 1492 1485 59.6 0.5 ␦CH3 + ␤CH of R1
90 1569 1559 1572 97.1 99.0 C8C9 + N3C12 + C C of R3
92 1592 1593 78.1 6.7 C C of R1,3 + C8C9 + N3C12
94 1592 1607 36.8 51.6 N3C12 + C C of R3
95 1643 1646 1700 221.5 1.4 C O
96 2936 2927 46.9 0.5 CH of CH3
98 2966 2983 12.5 0.6 CH of CH3
107 3070 3087 37.6 0.9 CH of R1,3
p-CBAP
24 416 408 16.9 0.1 C–Cl + ␳R3
26 443 437 41.8 1.6 ␯R2
28 503 496 5.2 0.2 ␯R1
29 512 509 14.2 0.6 ␯R3
30 589 569 24.5 2.0 ␣C7C8C9
34 627 623 41.7 0.6 ␣R1 + ␣C7N1N2
37 684 683 17.1 0.2 ␯R1 + ␥CH of R1
39 698 703 25.1 0.4 ␣R3 + ␣N3C12C13
40 716 721 15.1 0.1 ␥CH of R1 + ␯R2
41 761 746 37.1 0.2 ␥CH of R1
43 825 827 815 19.1 0.4 ␥CH of R1
46 870 878 856 12.4 3.2 ␤imine
48 929 913 13.6 0.3 C7C8 + C9N2 + ␳CH3
52 942 953 0.1 0.0 ␥CH of R1
53 993 979 0.2 2.1 ␪R1
54 967 981 9.2 0.5 ␥CH of imine
55 1004 1007 990 31.6 1.5 ␪R3
58 1041 1039 1031 18.6 3.1 ␳CH3
60 1079 1087 1063 94.5 5.6 ␤CH of R3 + C–Cl
64 1131 1122 128.8 0.7 ␳CH3
65 1148 1135 45.1 10.0 ␳CH3 + C7N1 + C8N3
67 1165 1156 4.9 12.5 ␤CH of R3
70 1238 1215 1204 25.7 31.1 C12C13 + ␤CH of R3
71 1277 1277 196.5 1.3 C1N1 + C8N3 + ␤CH of R1,3
73 1301 1290 62.8 2.5 C C of R1,3 + ␤CH of R1
76 1303 1316 42.5 2.2 C C of R1 + C7N1 + ␤CH of R1
77 1339 1361 23.3 1.6 ␤CH of CH3 +␤CH of imine
78 1357 1372 74.3 2.4 ␤CH of imine
79 1379 1392 105.0 0.2 C7C8 + N2C9 + C9C10 + ␤CH of CH3 + ␤CH of R3
80 1404 1402 16.4 7.6 C7C8 + N2C9 + C9C10 + ␤CH of CH3 + ␤CH of R3
81 1416 1416 1422 17.0 2.1 ␤CH of CH3
84 1453 1454 22.1 0.7 ␦CH3
86 1489 1478 76.1 4.3 ␤CH of R3
88 1487 1485 69.3 0.5 ␦CH3 + ␤CH of R1
90 1568 1568 1573 13.7 98.8 C8C9 + N3C12 + C C of R3
92 1594 1593 181.5 5.6 C C of R1,3 + C8C9 + N3C12
94 1609 1608 17.7 38.2 N3C12 + C C of R3
95 1650 1650 1700 224.1 1.2 C O
96 2933 2927 47.8 0.3 CH of CH3
106 3067 3086 37.2 0.6 CH of R1,3
a
Mode numbers are extracted from the output result of the B3LYP calculation. Vibrational frequencies (Freq.) are in cm−1 ; the calculated IR intensities (IIR ) are in km mol−1 ;
the calculated Raman scattering intensities (IRaman ) are in arbitrary units as in Eq. (1). R, ring; ␣, angle bending; ␤, in-plane bending; ␥, out-of-plane bending; ␻, wagging; ␯,
puckering; ␪, breathing; ␦, scissoring; ␶, torsion; ␳, rocking; , stretching.

CBIAAP are ascribed to the C N stretching modes coupling partly
with C C stretching of No. 3 rings. We confirm that the Raman
scattering activities of these compounds are closely related to the
pi-electron conjugated moieties linked through the Schiff base
imines.
The bands observed at 1039 and 1128 cm−1 in o-CBIAAP, 1023
and 1128 cm−1 in m-CBIAAP, or 1039 and 1131 cm−1 in p-CBIAAP
are designated to the methyl rocking vibrations in FT-IR spec-
tra. The theoretically computed values of 1031 and 1122 cm−1
show excellent agreements with the recorded ones. The weak
peaks at about 1455 cm−1 in these FT-IR spectra are designated
to the methyl C–H scissoring vibrations, the experimental and
theoretical results are consistent with each other. The medium
peaks observed at 1488 cm−1 in o-CBIAAP, 1492 cm−1 in m-CBIAAP
and 1485 cm−1 in p-CBIAAP are ascribed to the mixed vibra-
tional modes of the methyl C–H scissoring and No. 1 ring C–H
in-plane wagging. The weak peaks observed at about 2935 cm−1
in these FT-IR spectra are ascribed to the methyl C–H stretch-
ing vibrations, which the theoretically computed bands are in
the bands of 2926–2982 and 3021–3055 cm−1 responding to
the methyl symmetrical and asymmetrical stretching vibrations,
respectively.
In low frequency region, these bands are mainly ascribed to
the wagging, rocking and torsional vibrations of the molecular
skeleton structures. In high frequency region, the C–H stretch-
ing vibrations are characterized by weak bands in the range of
2926–3127 cm−1 . The methyl C–H stretching vibrations have been
stated above. The aromatic C–H stretching vibrations are nor-
mally found in the band of 3063–3127 and observed at about
3068 cm−1 .
 R. Zhang et al. / Spectrochimica Acta Part A 75 (2010) 1115–1124
Fig. 1. IR spectra of the title compounds: (a) observed; (b) simulated.
Although the title compounds can be differentiated by
some slight infrared spectral characteristics, they can be distin-
guished easily and clearly by their Raman spectra. As shown
in Fig. 2, the Raman spectral features of the compounds
are more obviously different from each other than those of
IRs. Some Raman spectral bands have been discussed above,
1121
Fig. 2. Raman spectra of the title compounds: (a) observed; (b) simulated.
and more detailed Raman assignments can be seen from
Table 2.
3.3. Thermodynamic properties
On the basis of theoretical harmonic frequencies obtained from
density functional calculations at B3LYP/6-31G(d) level, the statisti-
cal standard thermodynamic functions, viz., heat capacities (Cp,m ),
1122 R. Zhang et al. / Spectrochimica Acta Part A 75 (2010) 1115–1124

Table 3
Thermodynamic properties of the title compounds at different temperatures.a .

T o-CBAP m-CBAP p-CBAP

        
Cp,m Sm Hm Cp,m Sm Hm Cp,m Sm Hm

200.00 245.16 531.18 28.57 245.19 529.97 28.51 245.18 530.93 28.59
250.00 296.02 591.33 42.10 296.07 590.13 42.04 296.05 591.09 42.12
298.15 345.10 647.68 57.54 345.14 646.49 57.48 345.10 647.44 57.56
350.00 396.19 707.03 76.77 396.19 705.84 76.71 396.15 706.79 76.79
400.00 442.23 762.98 97.74 442.22 761.79 97.68 442.17 762.73 97.76
450.00 484.35 817.54 120.92 484.32 816.35 120.86 484.27 817.28 120.94
500.00 522.36 870.57 146.11 522.32 869.38 146.05 522.26 870.30 146.12
550.00 556.45 921.99 173.09 556.40 920.78 173.03 556.35 921.71 173.10
600.00 586.98 971.74 201.69 586.94 970.53 201.63 586.89 971.45 201.70
  
a
Temperatures (T) are in K; standard heat capacities (Cp,m ) are in J mol−1 K−1 ; standard entropies (Sm ) are in J mol−1 K−1 ; standard enthalpy changes (Hm ) are in kJ mol−1 .

entropies (Sm ), and enthalpy changes (H  (0 → T )) for the title 3.4. Nonlinear optics
m
compounds were obtained and listed in Table 3. The scaling factor
for the vibrational frequencies is also 0.9614. The calculations of molecular dipole moment (), linear polariz-
From Table 3, we can find that the standard heat capacities, ability (˛) and first-order hyperpolarizability (ˇ) from the Gaussian
entropies and enthalpy changes are increasing with temperatures output have been stated in detail previously [49–51], and DFT
ranging from 200 to 600 K due to the fact that the molecular vibra- has been extensively used as an effective method to investigate
tional intensities are increasing with temperatures. These empirical the organic NLO materials. In this work, the related nonlinear
relations of the thermodynamic functions vs. temperatures were optical values of the studied molecules were calculated by the
fitted respectively by quadratic, linear and quadratic formulas, and DFT/B3LYP/6-31G(d) method using Gaussian 03W and listed in
these corresponding fitting factors are all beyond 0.999, and the Table 4.
corresponding fitting equations are as follows: The total static dipole moment (0 ), polarizability (˛0 ) and
first-order hyperpolarizability (ˇ0 ) calculated as in the cor-
• For o-CBIAAP: responding equations (4) and (5) are 2.059 Debye, 37.220 Å3
and 1.894 × 10−29 cm5 /esu for o-CBIAAP, 1.630 Debye, 37.458 Å3
and 1.864 × 10−29 cm5 /esu for m-CBIAAP, 2.171 Debye, 38.269 Å3

Cp,m = −7.4624 + 1.3827T − 6.5013 × 10−4 T 2
and 1.003 × 10−29 cm5 /esu for p-CBIAAP, respectively. The val-
ues of ˛0 and ˇ0 of the compounds are greater than the
ones of urea (˛0 = 3.8312 Å3 and ˇ0 = 3.7289 × 10−31 cm5 /esu cal-

Sm = 317.38 + 1.1021T culated with the same method). Theoretically, the first-order
hyperpolarizabilities of o-CBIAAP, m-CBIAAP and p-CBIAAP are
respectively of 50.8, 50.0 and 26.9 times magnitude of urea. That

Hm = −6.7743 + 0.08761T + 4.3444 × 10−4 T 2 is to say, the compounds are probably good candidates of NLO
materials.
Many research works have indicated that the frontier molecular
• For m-CBIAAP:
orbitals (FMOs) have significant effect on material NLO properties
[42,51,57–59]. In quest of the NLO characteristics, the surfaces of

Cp,m = −7.3378 + 1.3822T − 6.4994 × 10−4 T 2 FMOs of the studied molecules were investigated and shown in
Fig. 3. We can see that the FMOs are mainly composed of atomic
p-electron orbitals. It is evident that the NLO properties of the
 compounds are caused by the charge-transferring characteristics
Sm = 316.19 + 1.1021T
of FMOs of the molecules. However, the correlation between the
first hyperpolarizabilities and energy gaps of HOMO–LUMO of the

Hm = −6.8343 + 0.08761T + 4.3444 × 10−4 T 2
Table 4
• For p-CBIAAP: The calculated dipole moments (Debye), static polarizability components (a.u.) and
first hyperpolarizability components (a.u.) for the title compounds.

Cp,m = −7.2671 + 1.3817T − 6.4944 × 10−4 T 2 o-CBIAAP m-CBIAAP p-CBIAAP

x 0.807 −1.332 −1.673

y 1.890 0.887 1.372
 z −0.124 −0.309 −0.175
Sm = 317.17 + 1.1020T ˛xx 393.963 401.346 433.132
˛yy 250.038 247.016 230.302
˛zz 110.268 110.740 112.098
ˇxxx −2485.651 2319.121 1482.446

Hm = −6.7624 + 0.08767T + 4.3432 × 10−4 T 2 ˇxxy −222.016 −710.888 −247.879
ˇxyy 233.015 −167.387 −247.657
ˇyyy 218.601 57.044 88.668
ˇxxz 276.383 198.187 137.754
Since they are isomers, the thermodynamic function values are ˇyyz −6.610 −54.568 −35.689
close to each other. All the thermodynamic data provide helpful ˇxzz 70.944 −78.735 −79.660
information to further study on the title compounds in the ther- ˇyzz 60.608 61.617 55.644
ˇzzz −57.300 −47.981 −40.238
mochemical field.
 R. Zhang et al. / Spectrochimica Acta Part A 75 (2010) 1115–1124
Fig. 3. Surfaces of FMOs for the studied molecules (orbital numbers are extracted from the output results of the B3LYP calculation).
studied molecules are not following with the empirically inverse
relationship reported previously [51,58,59].
4. Concluding remarks
The vibrational modes, thermodynamics and nonlinear opti-
cal properties for three monochloroine substituted benzyli-
deneaminoantipyrines have been investigated by a combined
experimental and theoretical approach.
Attempts have been made for the proper frequency assign-
ments from these IR and Raman spectra in this work. Density
functional calculations at B3LYP/6-31G(d) level were carried out
to study the equilibrium geometries, vibrational spectra, thermo-
dynamics and NLO properties for the studied molecules. Most of
the optimized bond lengths are slightly longer than the experi-
mental values agreeing within 0.038 Å, and the optimized bond
angles are slightly different from the experimental values agreeing
within 5.8◦ . The IR and Raman spectra of the title compounds have
been ascribed assigned to the molecular structures with the help
of theoretical calculations. During the ascribing process, we can
find that the theoretical harmonic frequencies are in good agree-
ment with these observed values. It is remarkable that ␲-electrons
conjugated moieties linked by Schiff base imines are responsible
for the excellent Raman scattering activities of the studied com-
pounds, which were confirmed accurately by the Raman spectral
assignments. The thermodynamic properties of the compounds
obtained from the harmonic frequencies of their optimized struc-
tures are similar to each other among the isomers. The nonlinear
optical properties revealed by theoretical calculations indicate that
the studied compounds are good candidates of nonlinear optical
materials.
We hope the results are of assistance in the quest of experimen-
tal and theoretical evidences for the title compounds as spectral
properties, reaction intermediates and NLO materials.
Acknowledgements
This work was supported by the Scientific Research Foundation
for Excellent Plan of Binzhou University (BZXYQNLG200704) and
Research Funds of Qufu Normal University.
1123
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.saa.2009.12.067.
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