Molecular structure, spectroscopic properties and quantum chemical calculations of a novel 2,2′-Dicarboxy-4,4′-(propane-2,2-di-yl)diphenol

Article abstract of DOI:10.1016/j.molstruc.2014.08.021

The synthesis, spectroscopic (IR, ¹H and ¹³C NMR chemical shifts) investigations of 2,2′-Dicarboxy-4,4′-(propane-2,2-di-yl)diphenol molecule have been confirmed. Molecular geometry, vibrational frequencies and gauge including atomic orbital (GIAO) ¹H and ¹³C NMR chemical shift values of the compound in the ground state have been calculated using the density functional method (DFT) with 6-311G++(d,p) basis set. The calculated values are in good agreement with the experimental values. The energetic behavior of the compound in solvent media has been examined using B3LYP method with the 6-311G++(d,p) basis set by applying the polarizable continuum model (PCM). The total energy of the compound decreases with increasing polarity of the solvent. Besides, molecular electrostatic potential (MEP), non-linear optical (NLO) properties of the compound have been investigated by using theoretical calculations.

Full text of DOI:10.1016/j.molstruc.2014.08.021

Journal of Molecular Structure 1076 (2014) 704–712
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Molecular structure, spectroscopic properties and quantum chemical
calculations of a novel 2,20-Dicarboxy-4,40-(propane-2,2-di-yl)diphenol
c
Fatma Aydın a, Gökhan Alpaslan b, , Hüseyin Ünver
⇑
a Department of Chemistry, Faculty of Arts and Science, Çanakkale Onsekiz Mart University, TR-17100 Çanakkale, Turkey
b Department of Medical Services and Techniques, Vocational School of Health Services, Giresun University, TR-28200 Giresun, Turkey
c Department of Physics, Faculty of Science, Ankara University, TR-06100 Tandog˘an, Ankara, Turkey
h i g h l i g h t s
ꢀ
ꢀ
ꢀ
ꢀ
The compound was characterized by spectroscopic methods (FT-IR and NMR).
Quantum chemical computations of title compound were performed with DFT/B3LYP/6-311++G(d,p) level.
The calculated results were compared with experimental results.
NLO and MEP analysis of the compound were studied.
a r t i c l e i n f o
a b s t r a c t
The synthesis, spectroscopic (IR, 1H and C NMR chemical shifts) investigations of 2,20-Dicarboxy-4,40-
(propane-2,2-di-yl)diphenol molecule have been confirmed. Molecular geometry, vibrational frequencies
and gauge including atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the compound in the
ground state have been calculated using the density functional method (DFT) with 6-311G++(d,p) basis
set. The calculated values are in good agreement with the experimental values. The energetic behavior
of the compound in solvent media has been examined using B3LYP method with the 6-311G++(d,p) basis
set by applying the polarizable continuum model (PCM). The total energy of the compound decreases
with increasing polarity of the solvent. Besides, molecular electrostatic potential (MEP), non-linear opti-
cal (NLO) properties of the compound have been investigated by using theoretical calculations.
Ó 2014 Elsevier B.V. All rights reserved.
13
Article history:
Received 23 June 2014
Received in revised form 24 July 2014
Accepted 11 August 2014
Available online 19 August 2014
Keywords:
Bisphenol A
Spectroscopy
DFT
MEP
NLO
Introduction
to store food products [9]. In additional, BPA ligands with different
bridging geometries have given rise to diverse covalent metal–
Carboxylated bisphenol compounds were first synthesized by
Wygant in 1959. The study was patented in 1962. This invention
relates to a group of multifunctional stabilized bisphenol com-
pounds [1]. Bisphenol A (BPA) is used in many plastic consumer
products including toys, water pipes, drinking containers, eyeglass
lenses, sports safety equipment, kitchen appliances, medical equip-
ment, and consumer electronics [2–4]. It is one of the highest vol-
ume chemicals produced worldwide, with over six billion pounds
produced each year [5]. Besides, they are widely used in the man-
ufacturing of epoxy resins and polycarbonates to produce different
everyday objects like water bottles, coatings or electronic devices
[6–8]. Recently, BPA and its derivatives are commonly used in
industry such as varnish for coating the inside walls of cans used
organic network structures [10,11].
By means of increasing development of computational chemis-
try in the past decade, the research of theoretical modeling of drug
design, functional material design, etc., has become much more
important than ever. Many significant chemical and physical prop-
erties of biological and chemical systems can be predicted from the
first principles by various computational techniques [12,13]. Cur-
rently, density functional theory (DFT) method has been accepted
as a popular post-HF approach for the computation of structural
characteristics, vibrational frequencies and energies of molecules
by the ab initio community [14] and for the efficiency and accuracy
with respect to the evaluation of a number of molecular properties
[15,16].
In this paper, we have been reported the synthesis and charac-
terization of a novel, 2,20-Dicarboxy-4,40-(propane-2,2-di-yl)diphe-
nol (Scheme 1) as well as theoretical studies on it using the
DFT/B3LYP/6-311++G(d,p) method. The aim of this study is to
⇑
Corresponding author. Tel.: +90 4543102905.
E-mail address: gokhan.alpaslan@giresun.edu.tr (G. Alpaslan).
http://dx.doi.org/10.1016/j.molstruc.2014.08.021
0022-2860/Ó 2014 Elsevier B.V. All rights reserved.

F. Aydın et al. / Journal of Molecular Structure 1076 (2014) 704–712
705
investigate molecular structure, vibrational frequencies and 1H and
13C NMR chemical shift values of the title compound, both experi-
mentally and theoretically. The properties of the structural geom-
etry, molecular electrostatic potential (MEP), frontier molecular
orbitals (FMO’s), and non-linear optical (NLO) properties for the
compound at the B3LYP/6-311++G(d,p) level were studied. And
so, these studies are valuable for providing insight into molecular
properties of BPA compounds.
vibrational bands have been made by using GaussView molecular
visualization program [20]. Additionally, the calculated vibrational
frequencies were clarified by means of the potential energy distri-
bution (PED) analysis and assignments of all the fundamental
vibrational modes using VEDA 4 program [21,22].
The 1H and 13C NMR chemical shifts were calculated within
GIAO approach [23,24] applying the same method and the basis
set as used for geometry optimization. The effect of solvent on
the theoretical NMR parameters was included using the default
model IEF-PCM (Integral-Equation-Formalism Polarizable Contin-
uum Model) [25] provided by Gaussian 09W. DMSO was used as
solvent in here. The calculated NMR chemical shifts were com-
pared with the experimental analogs recorded with respect to
TMS as the reference for chemical shielding.
Experimental and computational methods
Synthesis
For the preparation of the 2,20-Dicarboxy-4,40-(propane-2,2-di-
yl)diphenol, bisphenol-A (2.28 g, 10 mmol) and ethyl acetoacetate
(1.3 mL, 10 mmol) was dissolved in acetonitrile (15 mL) and
Bi(NO3) (0.187 g, 0.5 mmol) and antimony trichloride (0.113 g,
0.5 mmol) was added to this solution. The resulting solution
refluxed for 3 h. After completion of the reaction, then allowed to
cool to room temperature. The solid material containing reduced
metal salt was removed by vacuum filtration and washed with ace-
tonitrile (2 ꢁ 10 mL). The combined filtrate was evaporated on a
rotary evaporator under reduced pressure to give the product
which was chromatographed over silica gel using ethyl acetate–
hexane (1:4) as the eluent to separate the product. It was crystal-
lized from ethyl acetate/dichloromethane as yellow crystals, m.p.
220–221 °C, 2.69 g (85%) yield. Found: C, 64.42; H, 5.16; O, 30.42.
Calc. For C17H16O6; C, 64.55; H, 5.10; O, 30.35%.
In order to investigate the energetic and dipole moments
behavior of the title compound in solvent media, we also carried
out optimization calculations in three kinds of solvents (chloro-
form, ethanol, and water) by using polarizable continuum model
(PCM) method [26–29]. To investigate the reactive sites of the
compound the molecular electrostatic potential was evaluated
using the B3LYP/6-311G++(d,p) method. The linear polarizability
and first hyperpolarizability properties of the compound were
obtained from molecular polarizabilities based on theoretical
calculations.
Results and discussion
Synthesis
Coumarins were obtained by Pechmann condensation, which
involves condensation of phenol with b-ketoesters using different
catalysts such as metal, metal salts, zeolites, and phosphotungstic
acid [30]. Cyclic products occurs from the reaction of phenols and
ethyl acetoacetate with catalysts. In studies, SbCl3 and metal salt
mixture is not used. Therefore, in this study, both SbCl3, and Bi
(NO3)3 are used together. However, we expect the product did
not occur. Consequently, Coumarin not occur, carboxylated bisphe-
nol formed. Substituted bisphenol was synthesized in moderate to
high yields via carboxylation of phenols with b-ketoesters by anti-
mony chloride and bismuth nitrate, as an efficient catalyst.
Instrumentation
The 1H and 13C NMR spectra were recorded on a Bruker
AVANCE-500 (400 MHz) spectrometer using tetramethylsilane
(TMS) as internal standart and Dimethyl sulfoxide (DMSO) as sol-
vent. Infrared absorption spectra were obtained from a Perkin
Elmer BX II spectrometer in KBr discs and were reported in cmꢂ1
units. Elementary analyses were performed on a Vario EL III CHNS
elemental analyzer. Melting points were measured on a Electro
Thermal IA 9100 apparatus using a capillary tube. Bisphenol-A,
ethyl acetate, acetonitrile, antimony trichloride, dichloromethane,
hexane were purchased from Aldrich (Germany).
Optimized structure
Computational procedures
The optimized molecular structure of the title compound was
calculated at the B3LYP/6-311G++(d,p) level by DFT method and
the cartesian coordinates of the title compound molecule are given
in Table 1a. Besides, the calculated geometric parameters were
listed in Table 1b and optimized molecule structure is shown in
Fig. 1. The molecule is not planar, since the dihedral angle between
two phenyl ring systems is 83.53°. The calculated double O33@C28
The DFT calculations with a hybrid functional B3LYP (Becke’s
three parameter hybrid functional using the LYP correlation func-
tional) at 6-311G++(d,p) basis set by using Berny method [17,18]
were performed with the Gaussian 09W software package [19].
The harmonic vibrational frequencies were calculated at the same
level of theory for the optimized structure. The assignments of
Scheme 1. 2,20-Dicarboxy-4,40-(propane-2,2-di-yl)diphenol.

706
F. Aydın et al. / Journal of Molecular Structure 1076 (2014) 704–712
Table 1b
and O37@C29 bond lengths in carboxyl groups were found as
1.206 Å and 1.207 Å, while the single C28AO32 and C29AO36 bond
lengths in ones are calculated as 1.378 Å, respectively. Similarly,
the calculated single C6AO30 and C23AO34 bond lengths in
hydroxyl groups were found as 1.351 Å. The CAC bond lengths in
phenyl rings of the title molecule were calculated at the interval
1.380–1.411 Å and the calculated C1AC10, C10AC11, C10AC19
and C10AC15 bond lengths were found as 1.540 Å, 1.546 Å,
1.540 Å and 1.546 Å, respectively. The C1AC10AC15, C1AC10AC19
and C19AC10AC15 bond angles were calculated as 107.86°,
109.26° and 112.17° for the compound, respectively. These bond
lengths and angles are in agreement with the literatures [31,32].
In this connection, Babu et al. [31] were recorded as
1.5339(16) Å, 1.5331(16) Å, 1.5398(15) Å and 1.5377(16) Å for
C10AC11, C10AC19, C10AC1 and C10AC15 bond lengths for
synthesized 30-Dinitrobisphenol A compound, respectively and
likewise, they were found as 107.24(9)° for C11AC10AC15 and
107.52(9)° for C1AC10AC19 bond angles.
The calculated some selected bond lengths, bond angles and torsion angles of the title
compound.
Parameters
DFT/6-311++G(d,p)
Bond lengths (Å)
C1AC10
C10AC19
C11AC10
C10AC15
C1AC2
C1AC8
C8AC7
C7AC6
C4AC6
1.540
1.540
1.546
1.546
1.410
1.383
1.411
1.410
1.402
1.380
1.351
1.474
1.206
1.378
1.351
1.206
C2AC4
C6AO30
C7AC28
C28AO33
C28AO32
C23AO34
C29AO37
Bond angles (°)
C1AC10AC19
C11AC10AC15
O33AC28AO32
C7AC6AO30
O34AC23AC24
O36AC29AO37
C1AC8AC7
109.26
107.54
120.20
125.25
116.20
120.20
122.59
IR studies
FT-IR spectrum of the investigated compound was measured in
the 4000–400 cmꢂ1 region using KBr pellet on a Bruker AVANCE-
500 spectrometer (Fig. 2a). The vibrational frequencies of the com-
pound were calculated by using B3LYP/6-311++G(d,p) method
(Fig. 2b). Determinations of the calculated vibrational bands have
been made by using GaussView molecular visualization program
Torsion angles (°)
C15AC10AC19AC26
C20AC19AC10AC1
C6AC7AC28AO32
173.14
ꢂ128.33
0.478
Table 1a
The cartesian coordinates of the title compound calculated at the B3LYP/6-311++G(d,p)
level.
[20]. In addition, theoretical vibrational frequencies of the title
compound were interpreted by means of PEDs using VEDA 4 pro-
gram [21,22]. Likewise, the assignments of the vibrational bands
in terms of PED by using the VEDA 4 program have been performed
by many researchers in the literature [22,33–35].
The assignments of the observed vibration bands have been
performed and compared with the calculated frequencies. The
experimental and calculated vibrational frequencies, and their
assignments are given in Table 2. Because of the states such as neg-
ligence of anharmonicity, incomplete inclusion of electron correla-
tion effects and basis set deficiencies, the calculated harmonic
vibrational frequencies become bigger than the observed ones
[36,37]. For this reason, the calculated wavenumbers are usually
scaled by scaling factor to compare with observed wavenumbers
and at the present work, the scaling factors are taken as 0.983
for frequencies less than 1700 cmꢂ1 and 0.958 for frequencies
higher than 1700 cmꢂ1 for B3LYP/6-311++G(d,p) level [37].
The title compound has ACOOH groups and contains the OAH,
C@O and CAO vibrational modes. The dimer forms of compounds
containing carboxyl groups (ACOOH) appear as very broad-strong
bands at the interval 2500–3300 cmꢂ1 in the IR spectra [38]. But, in
this study, as seen from Fig 2a, the mentioned region is not
included a very broad-strong band. This situation indicates to
monomer form of the title compound. Besides, the OAH group
has three vibrations as stretching, in-plane and out-of-plane bend-
ing vibrations. The OAH stretching band in carboxyl group is
observed at 3429 cmꢂ1. Similarly, hydroxyl OAH stretching band
is found 3246 cmꢂ1. These different between the OH stretching
vibration modes in carboxyl and hydroxyl groups are due to intra-
molecular hydrogen bonding interaction. These bands have been
calculated as 3610 cmꢂ1 and 3537 cmꢂ1 for optimized structure,
respectively. In additional, we noted that the experimental results
belong to the solid phase and theoretical calculations belong to the
gas phase. In the solid state the experimental results are related to
Parameters
x (Å)
2.366353
y (Å)
z (Å)
C1
C2
H3
C4
H5
C6
C7
C8
4.976822
6.203756
6.222715
7.393641
8.329516
7.425379
6.214304
5.015630
4.117029
3.675090
2.462560
2.262150
2.609075
1.573237
3.385955
3.308709
2.441779
4.178908
3.838506
3.565323
3.247067
3.682399
4.090796
4.370993
4.689184
4.249109
4.487615
6.091992
3.359676
8.639053
8.550588
7.293796
5.075573
4.242954
4.025070
3.485509
3.014106
3.254109
7.113418
3.859413
3.881878
4.193480
3.529855
3.553345
3.135853
3.108085
3.471348
3.430615
4.217042
4.302433
3.338533
5.047383
4.587073
3.091235
2.136823
3.262061
2.997293
5.589748
5.815540
5.013554
7.090215
8.184035
7.962075
8.807202
6.701382
6.567996
2.722181
7.168248
2.813829
2.556470
2.369970
2.694778
9.452202
9.497153
8.438414
6.253524
8.389487
2.134963
3.060994
4.099802
2.455390
3.000369
1.110054
0.386963
1.038453
0.438387
3.108605
2.152522
1.677507
1.367314
2.719186
4.128658
3.603153
4.652360
4.873881
3.788514
5.126352
5.778082
5.721900
4.929996
3.574129
2.975856
3.024301
1.974586
ꢂ1.030907
7.158596
0.611165
ꢂ0.319901
ꢂ1.607550
ꢂ1.680891
5.370775
6.314918
7.679309
7.865891
8.618660
ꢂ2.529800
H9
C10
C11
H12
H13
H14
C15
H16
H17
H18
C19
C20
H21
C22
C23
C34
H25
C26
H27
C28
C29
O30
H31
O32
O33
O34
H35
O36
O37
H38
H39

F. Aydın et al. / Journal of Molecular Structure 1076 (2014) 704–712
707
Fig. 1. The optimized structures of 2,20-Dicarboxy-4,40-(propane-2,2-di-yl)diphenol molecules on B3LYP/6-3111++G(d,p) basis set.
Fig. 2. (a) Experimental and (b) theoretical FT-IR spectra of the title compound.
molecular packing, but in the gas phase the isolated molecules are
considered in the theoretical calculations. The C@O stretching
band give rise to vibration between 1870 and 1540 cmꢂ1 in which
the position of C@O stretching band depends on the physical state,
electronic and mass effects of neighboring substituents, conjuga-
tions and intra-intermolecular hydrogen bonding interactions.
[38–42]. The C@O stretching band found as in Fig. 2 found as
1628 cmꢂ1. Likewise, in the IR spectrum, the observed bands at
1106 and 1080 cmꢂ1 can be assigned to CAOH stretching modes
in carboxyl groups. These values are calculated 1066 and

708
F. Aydın et al. / Journal of Molecular Structure 1076 (2014) 704–712
Table 2
Comparison of the experimental and calculated vibrational frequencies (cmꢂ1).
Assignmentsa
(%PEDb)
Experimental IR (cmꢂ1
)
Calculated IR (cmꢂ1
)
B3LYP/6-311++G(d,p)
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
carboxyl(OH) (86)
carboxyl(OH) (86)
hydroxyl(OH) (92)
hydroxyl(OH) (92)
phenyl(CH) (92)
phenyl(CH) (92)
as(CH3) (87)
as(CH3) (82)
as(CH3) (99)
as(CH3) (88)
s(CH3) (100)
s(CH3) (100)
(C@O) (84)
(C@O) (84)
phenyl(CC) (50)
phenyl(CC) (40)
t(CC) (12) + b(HCC) (47)]phenylrings
3429
3429
3246
3246
3031
3031
2969
2969
2969
2969
2827
2827
1628
1628
1580
1580
1530
1479
1479
1411
1371
1322
1322
1256
1256
1222
1170
1170
1154
1102
928
3610.38
3610.26
3538.39
3537.80
3037.46
3037.33
2973.57
2973.23
2968.86
2965.18
2906.39
2901.72
1715.01
1714.22
1588.15
1587.97
1499.68
1471.53
1464.17
1397.06
1375.58
1323.07
1322.91
1252.12
1255.42
1216.60
1163.81
1161.18
1147.17
1106.93
931.71
[
d (CH3) (73)
d (CH3) (67)
bs(CH3) (36)
t
phenyl(CC) (12) + b(HOC) (22) + bphenyl(HCC) (15)
[t(CC) (18) + b(HCC) (23)]phenyl
[t
(CC) (18) + b(HCC) (23)phenyl
bphenyl(HOC) (22)
bphenyl(HOC) (20) + b(HCC) (23)phenyl
t
[b(HCC) (47) +
[b(HCC) (42) +
t
t
t
t
t
t
s(C1C10C19) (20) + q(CH3) (11)
t
t
(CC) (11)]phenyl
(CC) (10)]phenyl
(C-CH3) (36)
(C-CH3) (20)
(C-CH3) (20) +
(C-CH3) (22) +
q
(CH3) (26)
s
(HCCC) (25)
903
890
870
908.56
888.10
867.98
(C1-C10,19) (20) + bring(CCC) (11)
(C-CH3) (11) + bring(CCC) (12)
s(HCCC) (79)
834
839.41
s(HCCC) (75)
834
837.03
t
c
c
(C1-OH) (20) +
(OCOC) (62)
(OCOC) (60)
t
(C1C10) (13) + bring(CCC) (11)
789
776
776
785.35
775.97
775.39
a
t
, stretching; s, symmetric; as, asymmetric; d, scissoring; b, in-plane bending;
c
, out of plane bending; q, rocking.
b
Potential energy distribution (PED), less than 10% are not shown.
1060 cmꢂ1 for the optimized structure. The aromatic CAH stretch-
ing, CAH in-plane bending and CAH out-of-plane bending
vibrations appear in 2900–3100 cmꢂ1, 1000–1500 cmꢂ1 and 700–
1000 cmꢂ1 frequency ranges, respectively [38]. The CAH stretching
bands for phenyl rings have been observed at 3031 cmꢂ1. This band
is calculated at 3037 cmꢂ1 with B3LYP, respectively. The CAH in-
plane bending vibrations are observed at the interval 1530–
1170 cmꢂ1 as the combined with other bands. Similarly, the CAH
out-of-plane bending vibration is arisen at 884 cmꢂ1. In our calcu-
lations the CAH in-plane bending vibrations are found as 1499,
1375 and 1163 cmꢂ1, while the CAH out-of-plane bending vibra-
tion is computed as 837 cmꢂ1 for the compound. The CC stretching
modes in aromatic rings can occur between 1600 and 1400 cmꢂ1 in
fingerprint region [38]. The observed bands at 1580, 1530, 1371,
1322 cmꢂ1 as combined with other vibrations modes can attribute
to CC stretching modes of phenyl rings. Additionally, the CCC in-
plane bending modes of phenyl rings are observed at 890 and
870 cmꢂ1. The asymmetric and symmetric vibrations for the CH3
group ofꢂ1the title compound were observed at 2969 cmꢂ1 and
Fig. 3. Correlaction graph of calculated and experimental frequencies of the title
compound.
2827 cm
,
respectively. In additional, the observed band at
NMR studies
1479 cmꢂ1 can be assigned to the scissoring mode of CH3 group.
The correlation graphics between the calculated and experi-
mental IR vibrational frequencies of the compound is presented
in Fig. 3 and correlation coefficient is obtained as 0.9957. As we
can see from the correlation graph in Fig. 3, the experimental val-
ues are in a good agreement with the calculation ones.
Nuclear magnetic resonance spectroscopy (NMR), the isotropic
chemical shift analysis allows us to identify relative ionic species
and to calculate reliable magnetic properties which provide the
accurate predictions of molecular geometries [43–46]. The opti-
mized molecular geometry of the title compound was obtained

F. Aydın et al. / Journal of Molecular Structure 1076 (2014) 704–712
709
Table 3
The calculated and experimental 1H and 13C NMR isotropic chemical shifts of the title compound.
Nucleus Exp. chemical shifts
(ppm) (in DMSO-d6)
Cal. chemical shifts
(ppm) (in gas)
Cal. chemical shifts
(ppm) (in DMSO)
Nucleus Exp. chemical shifts
(ppm) (in DMSO-d6)
Cal. chemical shifts
(ppm) (in gas)
Cal. chemical shifts
(ppm) (in DMSO)
C1
C2
C4
C6
C7
C8
10C
11C
15C
19C
20C
22C
23C
24C
26C
28C
29C
142.66
141.06
122.52
150.75
119.50
139.99
41.53
148.05
144.17
122.61
165.79
113.85
135.17
48.13
149.00
144.89
122.25
165.40
114.15
135.00
48.39
H3
H5
H9
7.36
7.05
7.71
1.68
1.68
1.68
1.68
1.68
1.68
7.71
7.05
7.36
10.85
10.85
12.34
12.34
7.04
6.91
8.35
1.79
1.58
1.20
1.20
1.79
1.58
8.35
6.91
7.04
8.39
8.39
5.89
5.89
7.19
7.00
8.34
1.84
1.62
1.23
1.23
1.84
1.62
8.34
7.00
7.19
8.66
8.66
6.65
6.65
H12
H13
H14
H16
H17
H18
H21
H25
H27
H31
H35
H38
H39
30.28
30.28
31.10
31.10
30.68
30.68
142.66
139.99
119.50
150.75
122.52
141.06
155.73
155.73
148.05
135.17
113.85
165.79
122.61
144.17
168.68
168.68
149.00
135.00
114.15
165.40
122.25
144.89
170.90
170.90
by using B3PLYP method with 6-311++G(d,p) basis set in DMSO
solvent with IEFPCM solvent model. Then, the proton and car-
bon-13 NMR chemical shifts were calculated at the same level by
using GIAO method. The calculated and experimental 1H and 13C
NMR chemical shift values of title molecule are listed in Table 3.
Additional, NMR chemical shift spectra of the title molecule are
given in Fig. 4.
Frontier molecular orbitals
The highest occupied molecular orbital (HOMO) and the lowest
unoccupied molecular orbital (LUMO) are named as frontier
molecular orbitals (FMOs). The FMO’s are very important in deter-
mining molecular properties such as electric, optic, UV–Vis spectra,
chemical reactions [48]. The distributions and energy levels of the
frontier molecular orbitals (FMOs) were computed at B3LYP/6-
311G++(d,p) level for the compounds and are shown in Fig. 5.
The calculations indicate that the title compound have 81 occupied
MOs. The HOMO is almost localized whole molecule excepting the
OH groups in carboxylic acid (ACOOH) and some hydrogen atoms
in phenyl and methyl groups. Similarly, the LUMO is mainly local-
ized whole molecule excepting methyl groups and some hydrogen
atoms in phenyl and AOH groups Both HOMO and LUMO are local-
ized over whole molecule, but for LUMO except methyl groups. The
HOMO–LUMO energy gap can be used magnitude of kinetic stabil-
ity [49]. The value of the energy gap between the HOMO and LUMO
is 4.497 eV and this large energy gap indicates that the title struc-
ture is stable.
As seen from Table 3, the carbon-13 NMR chemical shift values
in aromatic rings and carbon atoms which are bonded to electro-
negative O atoms are observed at the interval 100–160 ppm. The
chemical shifts of the C28 and C29 carbon atoms which bonded
to two O atoms in carboxyl groups are observed at 155.73 ppm.
Similarly, the chemical shifts of the C6 and C23 atoms which are
bonded to one O atom of hydroxyl groups are observed at
150.75 ppm. The calculated values for the C28, C29, C6 and C23
atoms are (in gas phase/DMSO) 168.68/170.90, 168.68/170.90,
165.79/165.40 and 165.79/165.40 ppm, respectively. For aromatic
carbons, the experimental and calculated 13C NMR chemical shifts
are between 142.66–119.50 ppm and 148.05–113.85/149.00–
114.15 ppm (in gas phase/DMSO), respectively. The carbon atoms
in methyl groups are shielded by their own hydrogen atoms and
therefore they give resonance signal in high field [47]. The C11
and C15 carbon atoms are given signal at 30.28 ppm. The calcu-
lated values of these atoms are 31.10 ppm (in gas phase) and
30.68 ppm (in DMSO), respectively. Likewise, for C10 atom, the
experimental and calculated 13C NMR chemical shifts values are
41.53 ppm, 48.13 ppm (in gas phase) and 48.39 ppm (in DMSO).
The hydrogen atom in the carboxyl groups has resonance in the
range 10–13.2 ppm [38]. The H38 and H39 atoms in carboxyl
groups of the title molecule are given resonance signal of
12.34 ppm. The calculated values of these hydrogen atoms are
5.89 ppm (in gas phase) and 6.65 ppm (in DMSO), respectively.
The protons in phenol groups give rise to signal at the interval
4–7.5 ppm, depending on concentration, solvent and temperature
[38]. But, the phenolic proton under intra-intermolecular hydrogen
bonding interaction gives resonance signal between 10 and
12 ppm [38]. The chemical shift values of the H31 and H35 atoms
in the title molecule is observed at 10.85 ppm. The observed reso-
nance signals between 6.68 and 7.71 ppm are corresponded to
chemical shifts of the protons in aromatic rings, while methyl pro-
tons are given signal at 1.63 ppm. The calculated chemical shifts
for aromatic and methyl protons are calculated are (in gas phase/
DMSO) 8.34/8.35, 7.04/7.19, 6.91/7.00 ppm and 1.79/1.84, 1.58/
1.62, 1.20/1.23 ppm, respectively.
Total energies in solvent media
In order to evaluate the energetic behavior of the compound in
solvent media, we carried out calculations in gas phase and three
kinds of solvent (water, ethanol, and chloroform). The calculated
total, HOMO and LUMO energies and dipole moment using the
PCM by B3LYP/6-311G++(d,p) are listed in Table 4. The molecules
which belong to the large value of the HOMO–LUMO gap are sta-
ble, while vice versa [50]. From Table 4, we can conclude that the
total molecular energies obtained by PCM method decrease with
the increasing polarity of the solvent, while the dipole moments
will increase with the increase of the polarity of the solvent. Like-
wise, energy value between HOMO and LUMO are increased with
the increase of the polarity of the solvent. According to these
results, the stability of the title compound increases in going from
the gas phase to the solution phase.
Molecular electrostatic potential
The molecular electrostatic potential V(r) that is created in the
space around a molecule by its nuclei and electrons is well
established as a guide to molecular reactive behavior. It is defined
by Eq. (1),

710
F. Aydın et al. / Journal of Molecular Structure 1076 (2014) 704–712
Fig. 4. 13C (bottom) and 1H (top) NMR chemical shift spectra of the title molecule.
Z
ðr0Þ
X
ZA
RA ꢂ r
q
real physical property, V(r) can be determined experimentally by
diffraction or by computational methods [56].
MEP at the B3LYP/6-311G++(d,p) optimized geometry was cal-
culated. MEP is shown in Fig. 6.
The negative (red) and the positive (blue) regions in the MEP
were related to electrophilic reactivity and nucleophilic reactivity,
respectively. As can be seen from Fig. 6, this molecule has several
possible sites for electrophilic attack. Negative electrostatic poten-
tial regions (red color) are mainly localized over the oxygen atoms.
The negative V(r) value is ꢂ0.060 a.u. for O33 atom. The deepest
VðrÞ ¼
ꢂ
dr0
ð1Þ
r0 ꢂ r
A
in which ZA is the charge of nucleus A, located at RA,
q
ðr0Þ is the elec-
tronic density function of the molecule, and r0 is the dummy inte-
gration variable [51,52]. The MEP have been used for explaining
and predicting relative reactivities sites for electrophilic and nucle-
ophilic attack, investigation of hydrogen bonding interactions,
molecular cluster and crystal behavior and the correlation and pre-
diction of a wide range of macroscopic properties [53–55]. Being a

F. Aydın et al. / Journal of Molecular Structure 1076 (2014) 704–712
711
Table 5
Calculated polarizability and first hyperpolarizability components (a.u.) for the title
compound.
Parameters
Value (a.u)
Parameters
Value (a.u)
axx
axy
axz
ayy
ayz
azz
310.5640504
ꢂ0.007216
bxxx
bxxy
bxyy
byyy
bxxz
byyz
bxzz
byzz
bzzz
b0
ꢂ0.1402044
334.8287502
0.2418654
108.2249306
0.1761345
23.2493691
191.0024243
0.0010995
183.709331
685.2758057
228.4252685
0.5400479
atotal
ꢂ0.0009309
34.9945842
0.1694636
D
a
18.6020377
altered in phase, frequency, amplitude or other propagation char-
acteristics from the incident fields [57]. NLO is at the forefront of
current research because of its importance in providing the key
functions of frequency shifting, optical modulation, optical switch-
ing, optical logic, and optical memory for the emerging technolo-
gies in areas such as telecommunications, signal processing, and
optical interconnections [58–61]. The total static dipole moment
Fig. 5. Molecular orbital surfaces and energy levels given in parentheses for the
HOMO and LUMO of the title compound computed at B3LYP/6-311G++(d,p) level.
(l), the linear polarizability (a) and the first hyperpolarizability
(b) using the x, y, z components are defined as [16,62]:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
l
a
¼
¼
lx2
þ
ly2
þ
lz2
ð2Þ
ð3Þ
Table 4
Calculated energies, dipole moments and frontier orbital energies of the title
compound.
axx
þ
ayy
3
þ
azz
Gas phase
= 1)
Chloroform
= 4.9)
Ethanol
= 24.55)
Water
= 78.39)
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
(e
(e
(
e
(e
2
2
2
b ¼ ðbxxx þ bxyy þ bxzzÞ þ ðbyyy þ bxxy þ byzzÞ þ ðbzzz þ bxxz þ byyz
Þ
Etotal (Hartree)
EHOMO (Hartree)
ELUMO (Hartree)
ꢂ1109.16351 ꢂ1109.17530 ꢂ1109.17928 ꢂ1109.17999
ꢂ0.23621
ꢂ0.07085
4.4997
ꢂ0.23644
ꢂ0.07099
4.5022
ꢂ0.23694
ꢂ0.07139
4.5049
ꢂ0.23705
ꢂ0.07148
4.5054
ð4Þ
It is well known that the higher values of molecular polarizabil-
ity and hyperpolarizability are important for more active NLO
properties. The polarizabilities and hyperpolarizability are
reported in terms of atomic units (a.u) and the calculated values
E
l
HOMO–ELUMO (eV)
(D)
0.629
0.750
0.810
0.822
have been converted by using 1 a.u3 = (0.529)3 Å3 for
a and
1 a.u = 8.641 ꢁ 10ꢂ33 cm5/esu for b [63]. To understand the NLO
properties of the title compound, the linear polarizability (a) and
the first hyperpolarizability (b) were calculated at the B3LYP/6-
311G++(d,p) level using Gaussian 09W program package and the
results obtained from calculation were given in Table 5. The calcu-
lated polarizability (a) and first hyperpolarizability (b) for the com-
pound are 33.806 Å3 and 3.841 ꢁ 10ꢂ30 cm5/esu, respectively. Urea
is one of the essential molecules used for determination of the NLO
properties of molecular systems. Therefore, it is used as reference
molecule in NLO studies. The calculated values of the title com-
pound are greater than those of urea (the
a and b of urea are
4.900 Å3 and 0.787 ꢁ 10ꢂ30 cm5/esu obtained by B3LYP/6-
311G++(d,p) method). The polarizability and first hyperpolarizabil-
ity for title molecule is approximately 17.3 and 29.4 times than
those of urea. These results indicate that title compound is a good
candidate of nonlinear optical material.
Fig. 6. Molecular electrostatic potential map calculated at B3LYP/6-311G++(d,p)
level.
Conclusions
positive point of V(r) is localized on the H38 and H39 atoms and
these values are almost +0.066 a.u. These sites give the information
about the region from where the compound can have intermolec-
ular interactions.
In this study, 2,20-Dicarboxy-4,40-(propane-2,2-di-yl)diphenol
has been synthesized and characterized by using IR and NMR spec-
troscopic techniques. The molecular structure, vibrational frequen-
cies, NMR chemical shifts, frontier molecular orbitals, total
energies in solvent media, MEP and NLO properties of the title mol-
ecule have been calculated at the DFT/B3LYP/6-311++G(d,p) level.
The calculated vibrational frequencies, 1H and 13C NMR chemical
shifts values are in a very good agreement with the experimental
Non-linear optical effects
Non-linear optical (NLO) effects arise from the interactions of
electromagnetic fields in various media to produce new fields

712
F. Aydın et al. / Journal of Molecular Structure 1076 (2014) 704–712
[25] E. Cancès, B. Mennucci, J. Tomasi, J. Chem. Phys. 107 (1997) 3032–3041.
[26] S. Miertus, E. Scrocco, J. Tomasi, Chem. Phys. 55 (1981) 117–129.
[27] V. Barone, M. Cossi, J. Phys. Chem. A102 (1998) 1995–2001.
[28] M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Comput. Chem. 24 (2003) 669–681.
[29] J. Tomasi, B. Mennucci, R. Cammi, Chem. Rev. 105 (2005) 2999–3093.
[30] B.C. Raju, T.H. Babu, J.M. Rau, Ind. J. Chem. 48B (2009) 120–123.
[31] S. Babu, C. Pathak, S. Uppu, C. Jones, F.R. Fronczekc, R.M. Uppua, Acta
Crystallogr. E67 (2011) o2556–o2557.
values. The MEP map shows that the negative potential regions at
V(r) are localized over oxygen atoms and positive ones are local-
ized on hydrogen atoms. The total energy of the compound
decreases with increasing polarity of the solvent. This study also
demonstrates that the title compound can be used as a good non-
linear optical material.
[32] S. Guieu, P. Brandao, J. Rocha, A.M.S. Silva, Acta Crystallogr. E68 (2012) o1404.
[33] G. Mariappan, N. Sundaraganesan, J. Mol. Struct. 1063 (2014) 192–202.
[34] J.M.D. Markovic, Z.S. Markovic, J.B. Krstic, D. Milenkovic, B. Lucic, D. Amic, Vib.
Spectrosc. 64 (2013) 1–9.
[35] H. Gökçe, S. Bahçeli, Spectrochim. Acta Part A 133 (2014) 741–751.
[36] A.E. Özel, S. Çelik, S. Akyüz, S. Keçel, Vib. Spectrosc. 53 (2010) 151.
[37] H. Gökçe, S. Bahçeli, Spectrochim. Acta Part A 116 (2013) 242–250.
[38] R.M. Silverstein, F.X. Webster, Spectroscopic Identification of Organic
Compound, sixth ed., John Willey & Sons, New York, 1998.
[39] B.H. Stuart, Infrared Spectroscopy: Fundamentals and Applications, John Wiley
& Sons, England, 2004.
Acknowledgment
The authors are grateful to the Scientific Research Project Office
of Giresun University, Turkey, for access to the Gaussian 09W pro-
gram package. (Project no: FEN-BAP-A-220413-61)
References
[40] S. Chandra, H. Saleem, N. Sundaraganesan, S. Sebastian, Spectrochim. Acta A74
(2009) 704–713.
[41] G. Varsanyi, Vibrational Spectra of Benzene Derivatives, Academic Press, New
York, 1969.
[42] H. Gökçe, S. Bahçeli, Spectrochim. Acta Part A 78 (2011) 803–808.
[43] L.G. Wade Jr., Organic Chemistry, sixth ed., Pearson Prentice Hall, New Jersey,
2006.
[44] R.J. Anderson, D.J. Bendell, P.W. Groundwater, Organic Spectroscopic Analysis,
The Royal Society of Chemistry, Sanderland, UK, 2004.
[45] H.O. Kalinowski, S. Berger, S. Braun, Carbon-13 NMR Spectroscopy, John Wiley
& Sons, Chichester, 1988.
[46] K. Pihlaja, E. Kleinpeter (Eds.), Carbon-13 Chemical Shifts in Structural and
Sterochemical Analysis, VCH Publishers, Deerfield Beach, 1994.
[47] A. Abbas, S. Bahçeli, H. Gökçe, M. Bolte, S. Hussain, M.K. Rauf, Spectrochim.
Acta Part A 116 (2013) 599–609.
[48] I. Fleming, Frontier Orbitals and Organic Chemical Reactions, Wiley, London,
1976.
[49] K.H. Kim, Y.K. Han, J. Jung, Theor. Chem. Acc. 113 (2005) 233.
[50] N. Özbek, G. Kavak, Y. Özcan, S. Ide, N. Karacan, J. Mol. Struct. 919 (2009) 154–
159.
[51] P. Politzer, P.R. Laurence, K. Jayasuriya, Environ. Health Perspect. 61 (1985)
191–202.
[52] P. Politzer, P. Lane, Struct. Chem. 1 (1990) 159–164.
[53] J.S. Murray, K. Sen, Molecular Electrostatic Potentials Concepts and
Applications, Elsevier Science B.V, Amsterdam, The Netherlands, 1996.
[54] A. Pirnau, V. Chis, O. Oniga, N. Leopold, L. Szabo, M. Baias, O. Cozar, Vib.
Spectrosc. 48 (2008) 289–296.
[55] H. Gökce, S. Bahceli, O. Akyıldırım, H. Yüksel, O.G. Kol, Lett. Org. Chem. 10
(2013) 395–441.
[56] P. Politzer, D.G. Truhlar, Chemical Applications of Atomic and Molecular
Electrostatic Potentials, Plenum, New York, 1981.
[57] Y.X. Sun, Q.L. Hao, W.X. Wei, Z.X. Yu, L.D. Lu, X. Wang, Y.S. Wang, J. Mol. Struct.:
Theochem. 904 (2009) 74–82.
[58] C. Andraud, T. Brotin, C. Garcia, F. Pelle, P. Goldner, B. Bigot, A. Collet, J. Am.
Chem. Soc. 116 (1994) 2094–2102.
[59] M. Nakano, H. Fujita, M. Takahata, K. Yamaguchi, J. Am. Chem. Soc. 124 (2002)
9648–9655.
[60] V.M. Geskin, C. Lambert, J.L. Bredas, J. Am. Chem. Soc. 125 (2003) 15651–
15658.
[1] J.C. Wygant, Patent, 1962, US 3035091 A.
[2] O. Takahashi, S. Oishi, Environ. Health Perspect. 108 (2000) 931–935.
[3] L.N. Vandenberg, R. Hauser, M. Marcus, N. Olea, W.V. Welshons, Reprod.
Toxicol. 24 (2007) 139–177.
[4] L.S. Birnbaum, J.R. Bucher, G.W. Collman, D.C. Zeldin, A.F. Johnson, T.T. Schug,
J.J. Heindel, Environ. Health Perspect. 120 (2012) 1640–1644.
[5] E. Burridge, Eur. Chem. News (2003) 14–20.
[6] H.G. Franck, Industrial Aromatic Chemistry: Raw Materials, Processes,
Products, Springer, Heidelberg, 1988.
[7] H. Zhang, H. Wu, Q. Tang, Reguxing Shuzhi 11 (1996) 43.
[8] T. Gruber, R. Nestler, W. Seichter, P. Bombicz, J. Mol. Struct. 1056–1057 (2014)
319–325.
[9] I. Rykowska, W. Wasiak, Acta Chromatogr. 16 (2006) 7–27.
[10] J.M. Tanski, T.P. Vaid, E.B. Lobkovsky, P.T. Wolczanski, Inorg. Chem. 39 (2000)
4756–4765.
[11] C.F. Lim, J.M. Tanski, J. Chem. Crystallogr. 37 (2007) 587–595.
[12] Y. Zhang, Z.J. Guo, X.Z. You, J. Am. Chem. Soc. 123 (2001) 9378–9387.
[13] H. Tanak, A. Ag˘ar, M. Yavuz, J. Mol. Mod. 16 (2010) 577–578.
[14] M. Kurt, T.R. Sertbakan, M. Özduran, Spectrochim. Acta A 70 (2008) 664–673.
[15] C. Ravikumar, I.H. Joe, V.S. Jayakumar, Chem. Phys. Lett. 460 (2008) 552–558.
[16] R. Zhang, B. Du, G. Sun, Y. Sun, Spectrochim. Acta A 75 (2010) 1115–1124.
[17] A.D. Becke, J. Chem. Phys. 98 (1993) 5648–5652.
[18] C. Peng, P.Y. Ayala, H.B. Schlegel, M.J. Frisch, J. Comput. Chem. 17 (1996) 49–50.
[19] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox,
H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E.
Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y.
Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S.
Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J.
Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L.
Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M.
Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A.
Pople, Gaussian 09, Revision D.01, Gaussian Inc., Wallingford, CT, 2009.
[20] R. Dennington II, T. Keith, J. Millam, GaussView, Version 5.0.9, Semichem Inc.,
Shawnee Mission, KS, 2009.
[61] D. Sajan, H. Joe, V.S. Jayakumar, J. Zaleski, J. Mol. Struct. 785 (2006) 43–53.
[62] H. Tanak, Comput. Theor. Chem. 967 (2011) 93–101.
[63] T. Rajamani, S. Muthu, M. Karabacak, Spectrochim. Acta Part A 108 (2013)
186–196.
[21] M.H. Jamróz, Vibrational Energy Distribution Analysis VEDA 4, Warsaw, 2004.
[22] M.H. Jamroz, Spectrochim. Acta Part A 114 (2013) 220–230.
[23] R. Ditchfield, J. Chem. Phys. 56 (1972) 5688–5691.
[24] K. Wolinski, J.F. Hilton, P. Pulay, J. Am. Chem. Soc. 112 (1990) 8251–8260.