The examination of molecular structure properties of 4,4′-oxydiphthalonitrile compound: combined spectral and computational analysis approaches

Article abstract of DOI:10.1080/00387010.2018.1544569

The synthesis process, X-ray diffraction analysis of its single crystal form and the structural properties of the 4,4′-oxydiphthalonitrile compound by Fourier transform infrared, nuclear magnetic resonance and ultraviolet-visible spectral methods were rep

Full text of DOI:10.1080/00387010.2018.1544569

Spectroscopy Letters
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The examination of molecular structure properties
of 4,4′-oxydiphthalonitrile compound: combined
spectral and computational analysis approaches
Serpil Eryılmaz, Nesuhi Akdemir & Ersin İnkaya
To cite this article: Serpil Eryılmaz, Nesuhi Akdemir & Ersin İnkaya (2019): The examination
of molecular structure properties of 4,4′-oxydiphthalonitrile compound: combined spectral and
computational analysis approaches, Spectroscopy Letters, DOI: 10.1080/00387010.2018.1544569
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SPECTROSCOPY LETTERS
https://doi.org/10.1080/00387010.2018.1544569
The examination of molecular structure properties of 4,40-oxydiphthalonitrile
compound: combined spectral and computational analysis approaches
a
b
c
_
Serpil Eryılmaz , Nesuhi Akdemir , and Ersin Inkaya
b
aDepartment of Physics Faculty of Arts and Sciences, Amasya University, Amasya, Turkey; Department of Chemistry Faculty of Arts and
c
Sciences, Amasya University, Amasya, Turkey; Central Research Laboratory, Amasya University, Amasya, Turkey
ABSTRACT
ARTICLE HISTORY
Received 16 August 2018
Accepted 1 November 2018
The synthesis process, X-ray diffraction analysis of its single crystal form and the structural proper-
ties of the 4,40-oxydiphthalonitrile compound by Fourier transform infrared, nuclear magnetic res-
onance and ultraviolet-visible spectral methods were reported in this study. Density functional
theory studies of the compound were carried out by designed modeling with the Becke three-par-
ameter hybrid functional combined with Lee-Yang-Parr correlation functional and 6-311G(d,p)
basis set. Some molecular structure parameters obtained theoretically were compared with those
obtained from the crystallographic analysis. Vibrational modes and wavenumbers with the aid of
the potential energy distribution analysis, carbon and proton chemical shift values with diversified
approaches and absorption wavelengths using Time-Dependent Density Functional and
Conductor-Like Polarizable Continuum Model in different solvent media were examined theoretic-
ally. The compatibility of spectral and theoretical results was evaluated by examining the correl-
ation coefficients. In addition, the frontier molecular orbitals energies, global reactivity parameters,
molecular electrostatic potential map, the potential for non-linear optical material and some
thermodynamic parameters at different temperature values of the 4,4’-oxydiphthalonitrile com-
pound were investigated at the same theoretical level.
KEYWORDS
DFT; FT-IR; NMR;
phthalonitrile; UV-Vis
Introduction
phthalonitrile-derived compounds. In this respect, a large
number of syntheses, spectral and theoretical characteriza-
tion studies have been performed to elucidate the structures
of the newly substituted phthalonitriles. Some of these were
carried out by George and Snow[17] for 3-nitrophthalonitrile,
Karadayı et al.[18] for 4-(1-Naphthoxy)phthalonitrile,
In 1896, Pinnow and Samann[1] published an article in
which they first described the formation of phthalonitrile. It
consists of a derivative of benzene with two adjacent nitrile
groups and is used as an intermediate or precursor in some
chemical synthesis. Phthalonitriles compose some high-tem-
perature polymers which have remarkable features such as
high glass transition temperatures, oxidative and thermal
stability, damp and fire resistance, and are preferred for
many high-tech applications in military and civilian
areas.[2,3] Phthalonitriles and substituted phthalonitriles are
used in the synthesis of phthalocyanines which have a wide
range of applications. Some of these applications can be sum-
marized in this kind: as a colorant with tones blue, green,
cyan; with a coloring feature in paint, automotive paint, jet
printing, inks, textiles and paper industry, as photoconductive
devices; in photocopying machines, as chemical sensors; in the
determination of toxic gases affecting vital life, as liquid crys-
tals; in many advanced technological processes, as a photosen-
sitizer element; in photodynamic treatments for medical
conditions, as catalysts, solar cells; in nanotechnology and non-
linear optical material design.[4–16]
Koysal et al.[19] for 4-(2-Methoxy-1-naphthylmethoxy)-
€
phthalonitrile, Senthilkumar and Anbarasan[20] for 4-meth-
ylphthalonitrile, Łapok et al.[21] for 5-tert-butyl-3-(trifluoro-
methyl)phthalonitrile, Akc¸ay et al.[22] for 4-[(4,5-Diphenyl-
4H-1,2,4-Triazol-3-yl) sulfanyl]benzene-phthalonitrile, Tereci
et al.[14] for 4-(1-formylnaphthalen-2-yloxy) phthalonitrile,
Ziminov et al.[23] for 4-(4-hydrazinylphenoxy)phthalonitrile,
Saka et al.[24] for 4-[2-(2,3-dichlorophenoxy)ethoxy]phthaloni-
trile, Akdemir[25] for 4-(2,3,5-trimethylphenoxy) phthalonitrile.
Density functional theory (DFT) has attracted the interest
of scientists working in the computational chemistry and in
different fields, owing to consistent results with experiments
and providing a good approximation of the established
modeling in the absence of experimental data.[26] So, DFT
methods and applications are used not only to elucidate the
chemical structure and properties of molecules but also to
determine spectroscopic parameters as vibrational frequen-
cies and modes, chemical shift values, absorption wave-
The use of phthalonitrile precursors for the synthesis of
phthalocyanines has made it valuable to investigate the lengths, g factors, and hyperfine structure constants.
CONTACT Serpil Eryılmaz
srpleryilmaz@gmail.com.tr
Department of Physics Faculty of Arts and Sciences, Amasya University, Amasya, 05100, Turkey
Supplemental data for this article can be accessed here.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lstl.
ß 2019 Taylor & Francis

2
S. ERYILMAZ ET AL.
ꢀ
Scheme 1. Chemical diagrams of starting materials (1) and (2), synthesis process of yields (3) and (4). i- DMF, Molecular sieve 4 Å, K2CO3, 40 C, N2, 96 h Starting
materials; 3-hydroxypropanenitrile (1), 4-nitrophthalonitrile (2) Yields: 4,40-oxydiphthalonitrile (3), 4-Hydroxyphthalonitrile (4). DMF: dimethylformamide; Å: ang-
strom; K2CO3: potassium carbonate; ꢀC: centigrade; h: hour.
The aim of this study is to investigate the physical and Materials and instrumentation
chemical properties of 4,40-oxydiphthalonitrile via spectro-
IR spectrum was recorded on a Perkin Elmer Frontier FT-IR
Spectrometer (Perkin Elmer pioneer scientific technologies,
USA) as KBr pellets. UV-Vis spectrums were recorded in
CHCl3, THF, DCM, EtOH, MeOH solvent media with a Perkin
Elmer Lambda 35 UV/Vis Spectrometer (Perkin Elmer pioneer
scopic and quantum mechanical methods and to provide a
preliminary knowledge for the other possible phthalonitrile
derivatives. For this purpose, in the following sections, the
synthesis process, the spectroscopic analysis, the results of
the established modeling by DFT/B3LYP method over 6-
311G(d,p) basis set when compared with the experimental
ones, and the results of the computational analysis obtained
are given for the 4,40-oxydiphthalonitrile compound.
1
scientific technologies, USA). H-NMR and 13C-NMR studies
were done on an Agilent 400/54 (400MHz) spectrometer
(Agilent, USA) in DMSO solvent media. 4-Nitrophthalonitrile
[36]
was synthesized according to the reported procedure.
All
other reagents and solvents were of reagent-grade quality and
were obtained from commercial suppliers. DMF was dried and
purified as described by Perrin and Armarego.[37]
Experimental details
Synthesis process of 4,40-oxydiphthalonitrile (3)
X-ray crystallography
The single-crystal X-ray data were collected on a Bruker D8
QUEST (Bruker, USA) diffractometer. All diffraction meas-
urements were performed at room temperature (296 K) using
graphite monochromated Mo-Ka radiation (k ¼ 0.71073 Å).
Reflection data were recorded in the rotation mode using the
x scan technique by using X-AREA software.[38] Unit cell
parameters were determined from least-squares refinement of
setting angels with h in the range 3.3ꢂ h ꢂ 28.3ꢀ. The struc-
ture was solved by direct methods using SHELXS-97[39]
implemented in WinGX[40] program suit. The refinement was
carried out by full-matrix least squares method on the pos-
itional and anisotropic temperature parameters of the non-
hydrogen atoms or equivalently corresponding to 190 crystal-
lographic parameters, using SHELXL-2014.[41] The molecular
graphic were done using ORTEP-3 for Windows.[40] Details
of the data collection conditions and the parameters of the
refinement process are given in Table 1.
3-hydroxypropanenitrile (6.3 g, 88.63 mmol) was dissolved in
dry DMF (125 mL) under nitrogen and 4-nitrophthalonitrile
(5.08 g, 29.36 mmol) and molecular sieve 4 Å (10.80 g) were
added. After stirring for 2 h, finely ground anhydrous potas-
sium carbonate (13.50 g, 97.831 mmol) was added in por-
tions during 3 h with efficient stirring. The reaction mixture
was stirred at 40 ꢀC under nitrogen for 96 h. The mixture
was then poured in to ice-water (300 g). The precipitate was
filtered off, washed with water until neutral and dried. The
crude product was extracted with chloroform (4 ꢁ 50 mL).
The combined organic extracts were washed with water and
dried with anhydrous Na2SO4 and evaporated to dryness.
The resulting product was washed with water and then
dried, yield 4,40-oxydiphthalonitrile (3) 0,098 g. The single
crystals were obtained in DMF at room temperature via
slow evaporation. The other filtrate was acidified to pH 3
with HCl and filtered off and washed with water until neu-
tral and then dried, yield 4-hydroxyphthalonitrile (4)
2.451 g. It was not necessary to purify the product more.
The spectral specifications of 4,4’-oxydiphthalonitrile (3)
and 4-hydroxyphthalonitrile (4) were consistent with litera-
ture values.[27–32]
Computational details
Computational analyses were performed by using Gaussian
09 molecular structure[42] and GaussView 5.0 visualization
programs.[43] The geometric optimization of the compound
was performed by the density functional theory (DFT)[44]
level Becke’s three parameter method with Lee, Yang, Parr
correlational functional (B3LYP)[45] with 6-311G(d,p)[46]
basis set. The geometric optimization of the compound 4,4’-
oxydiphthalonitrile was carried out on the resulting molecu-
lar structure with crystallographic analysis. Vibrational fre-
quencies were calculated at the B3LYP/6-311G(d,p) level
The phthalonitrile derivatives are generally prepared via
aromatic nucleophilic substitutions.[27,33,34] Although our
primary aim was to obtain a 4-(2-cyanoethoxy)phthalonitrile
(5), the phthalonitrile derivative was not synthesized
(Scheme 1). Hydroxyphthalonitrile, oxydiphthalonitrile, and
benzene nitrile compounds were observed in these
reactions.[27–32,35]

SPECTROSCOPY LETTERS
3
Table 1. Crystallographic data and structure refinement parameters for the
4,40-oxydiphthalonitrile compound. The table contains information on the
characteristic properties of the single crystal form of the compound and
the refinement process by examined it with X-ray single crystal diffrac-
tion technique.
CCDC deposition
Colour/Shape
Chemical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
Unit cell parameters
a, b, c (Å)
1440732
Yellow
C16H6N4O1
270.25
296
0.71073 Mo-Ka
Triclinic
P-1
Figure 1. The molecular structure of the 4,40-oxydiphthalonitrile showing the
atom-numbering scheme. Displacement ellipsoids have been shown at the 20%
probability level. Hydrogen atoms have been shown as small spheres of arbi-
trary radii.
7.159 (2), 8.287 (3), 11.128 (3)
102.635 (15), 94.717 (17), 90.980 (17)
641.6 (4)
a, b, c (ꢀ)
Volume (Å3)
Z
2
Dcalc (g/cm3)
1.399
0.09
276
Table 2. Hydrogen-bond geometry for the 4,40-oxydiphthalonitrile compound.
In the crystal structure of the compound, there are two C—HꢆꢆꢆN-type inter-
molecular hydrogen bonds.
l (mmꢅ1
F(000)
)
Crystal size (mm3)
Diffractometer
0.11 ꢁ 0.09 ꢁ 0.07
Bruker APEX-II CCD
ꢅ9 ꢂ h ꢂ 9,ꢅ11ꢂ k ꢂ 11,ꢅ14ꢂ l ꢂ 14
3.3ꢂ h ꢂ 28.3
D—HꢄꢄꢄA
D—H (Å)
0.93
0.93
HꢄꢄꢄA (Å)
DꢄꢄꢄA (Å)
3.451 (2)
3.359 (2)
D—HꢄꢄꢄA (ꢀ)
C7—H7ꢄꢄꢄN2i
C16—H16ꢄꢄꢄN1ii
2.59
154
Index ranges
h range for data collection (ꢀ)
Reflections collected
Independent/observed reflections
Rint
2.46
162
33,009
3198/2371
0.040
Symmetry codes: (i) 1-x, 1-y, 1-z; (ii) –x, -y, 1-z
Å: angstrom unit; ꢀ: degree.
Refinement method
Final R indices [I > 2r(I)]
R indices (all data)
Goodness-of-fit on F2
Dqmax, Dqmin (e/Å3)
Full-matrix least-squares on F2
R1 ¼ 0.0425, wR2 ¼ 0.1011
R1 ¼ 0.0660, wR2 ¼ 0.1187
1.04
Results and discussion
0.18, ꢅ0.18
Description of the single-crystal structure
Å; angstrom unit; ꢀ; degree.
The 4,40-oxydiphthalonitrile molecule crystallizes in triclinic
space group P-1, with one symmetrically independent mol-
ecule. The molecular structure of the 4,40oxydiphthalonitrile
is presented in Figure 1. The title molecule contains two
phthalonitrile ring systems, linked by O atom. Two phthalo-
nitrile ring exhibits normal geometry and is planar.
theoretically and process the determination of the vibra-
tional modes were performed by the potential energy distri-
bution (PED) analysis using the VEDA 4 program.[47] Since
the spectral results are anharmonic, and the theoretical
results give harmonic vibrational frequency values, the calcu-
lated values were scaled with 0.9682[48] to prevent systematic
errors. Predicting proton and carbon NMR chemical shift
values of 4,4’-oxydiphthalonitrile compound and an internal
standard tetramethylsilane (TMS) were determined with
Continuous Set of Gauge Transformations (CSGT),[49]
Gauge-Independent Atomic Orbital (GIAO)[50] and
Individual Gauges for Atoms in Molecules (IGAIM)[49a,49b]
approaches and dimethyl sulfoxide (DMSO) as the solvent.
The molecular absorption spectral parameters of the com-
pound were investigated with Time-dependent density func-
tional (TD-DFT), B3LYP hybrid functional and 6-311G(d,p)
basis set in gaseous phase, and different solvent media using
Conductor-Like Polarizable Continuum Model (CPCM)[51]
solvent model. The calculated absorption wavelengths were
evaluated together with the spectral results; also excitation
energies (eV), oscillator strengths (f), and the major contri-
bution to probable orbital transitions were investigated. In
later sections of the paper, frontier molecular orbital energy
values and some reactivity parameters in solvent media with
different polarities were investigated with TD-DFT/B3LYP/
6-311G(d,p) method. Besides molecular electrostatic poten-
tial map (MEP), NLO properties with the values of dipole
moment, mean polarizability, and first-order hyperpolariz-
ability and the variation of thermodynamic parameters such
as heat capacity, entropy and enthalpy change at different
temperatures from 100 to 800 K were examined theoretically
for the 4,4’-oxydiphthalonitrile compound.
The dihedral angle of two phthalonitrile groups is 61.16ꢀ.
The CꢃN bond lengths C4ꢃN1, C5ꢃN2, C13ꢃN3, and
C14ꢃN4 are 1.1406(19) Å, 1.144(2) Å, 1.149(2) Å, and
1.1401(19) Å, respectively. These values show good agree-
ment with literature.[52,53] Similarly, the C8—O1 and C9—
O1 lengths are 1.3814(16) and 1.3868(16), respectively. The
bond angle values of N1ꢃC4—C3, N2ꢃC5—C6, N3ꢃC13—
C12, and N4ꢃC14—C15 are 179.41(17)o, 177.34(17)o,
177.07(18)o, and 178.73(16)o, respectively, these values are
observed to be linear. In the crystal structure of 4,40-oxy-
diphthalonitrile, there are two hydrogen bonds. One of them
[54]
2
ð
Þ
C7—H7ꢄꢄꢄN2 appear with graph set R2 10 .
All details
about available hydrogen bonds are given in Table 2 and
Figure 2.
Optimized structure analysis
The molecular geometry of the compound obtained as a
result of single crystal structure analysis has been the start-
ing point of the optimization process. Some parameters of
the optimized molecular structure formed by the selected
theoretical method and basis set are compared with the val-
ues obtained from X-ray analysis and the results are tabu-
lated in Table 3. Carbon-nitrogen triple bond lengths
specific to phthalonitrile groups; C4ꢃN1, C5ꢃN2, C13ꢃN3,
C14ꢃN4, was determined as 1.154 Å with theoretical level.

4
S. ERYILMAZ ET AL.
Figure 2. A partial packing diagram of the crystal structure of the 4,40-oxydiphthalonitrile, showing the intermolecular C—HꢆꢆꢆN hydrogen bonds. The hydrogen
bonds have been shown as the dashed lines.
In similar phthalonitrile studies, these lengths were recorded GaussView[43] programs were used in interpreting assign-
as 1.155 and 1.156 Å when calculated with the DFT/B3LYP ments at the vibrational modes. The results of the compari-
and 6-311þþG(d, p) basis set,[13] 1.154 and 1.155 Å when son of experimental and theoretical spectral values are given
calculated with the basis set 6-311 þ G (d).[15] O1–C8,
in Table 4. The experimental and simulated spectrums
O1–C9 bond lengths are 1.376, 1.374 Å in this article,
whereas 1.377 Å for 6-31G(d,p) basis set in another art-
icle.[14] The C–CꢃN bond angles were calculated as 178.55ꢀ
on average and it is seen that have almost linear bond angle
formed by the selected basis set method which plotted on
the transmittance (%) against the wavenumbers (cmꢅ1) are
shown in Figure 3.
The compound 4,40-oxydiphthalonitrile has 27 atoms and
values both theoretically and experimentally. The theoretical 75 fundamental modes of vibration; of which 26 are stretch-
C–C–H bond angle values are in good agreement with each ing, 25 are bending, 24 are torsion. Symmetric and asym-
other and with experimental values. In general, the theoret- metric C–H stretching vibrations have recorded at
3102–3038 cmꢅ1 in the IR spectrum, as conformably with
ically obtained geometric parameters of the compound have
satisfactory results with crystallographic values. As seen in
Table 3, the greatest difference between the optimized struc-
the 3100–3000 cmꢅ1 range where the C–H stretching band
is observed in the aromatic groups.[57–59] This spectral band-
ture parameters and the crystallographic values belongs to
C–H bond lengths with a value of 0.152 Å. This difference
can be attributed to the fact that in the crystallographic ana-
lysis process the X-rays detect the electron density instead of
the nucleus and therefore the hydrogen atoms have low
scattering factors.[54–56] The atom-by-atom superimposition
of the theoretical molecular structure DFT/B3LYP/6-
311G(d,p) (red) with the X-ray molecular structure (black)
of the 4,40-oxydiphthalonitrile compound is shown in S.1 in
the Supplemental Material section. The compliance between
experimental and theoretical values is represented by the
graphs of correlation S.2 and S.3 given in the Supplemental
Material section and R2 value (without the values C–H) is 0.
9907 for bond lengths, 0.9964 for bond angles.
width observed in the spectrum of the compound indicates
that the presence of nitrile groups does not cause a signifi-
cant change in this region. The theoretical values of pure
C–H stretching vibrations were determined with the contri-
bution of 99–60% PED in the range of 3113–3096 cmꢅ1. In
plane-bending and out-of-plane bending/torsional C–H
vibrations were observed in the range of 1472–1071cmꢅ1
,
953–827 cmꢅ1 with the contribution of 21–10%, 65–30%
PED as pure and mixed modes. In a similar paper, these
mode intervals were recorded as 1500–1000 cmꢅ1 and
1000-700 cmꢅ1 [14]
.
The CꢃN stretching peak was observed as spectral at
2232 cmꢅ1, theoretical at 2274–2268 cmꢅ1 mixed with low
ratio (11–10%) carbon-carbon vibration modes according to
PED analysis. Both spectral and theoretical values are con-
sistent with typical cyano group frequency values, which are
expected to give a sharp peak at 2210–2280 cmꢅ1 based on
their large dipole moments. In some other studies involving
Vibrational spectral and modes analysis
The FT-IR spectral data and scaled wavenumbers which cal-
culated with the B3LYP/6-311G(d,p) were investigated to the phthalonitrile moiety ,the sharp CꢃN stretching vibra-
examine the vibrational spectral behavior of the compound. tion peaks were recorded at 2234, 2258 cmꢅ1 for 6-
The PED analysis performed with VEDA 4[47] and 31G(d),[16] 2230, 2264 cmꢅ1 for 6-311G(d,p),[25] 2238,

SPECTROSCOPY LETTERS
5
Table 3. Continued.
Table 3. Experimental and theoretical values of molecular geometrical param-
eters for the 4,40-oxydiphthalonitrile compound. Experimental values represent
X-ray analysis data, theoretical values represent molecular structure parameters
optimized with Becke, three-parameter, Lee-Yang-Parr/6-311G(d,p) level
of theory.
Parameters
Experimental
120.4
Theoretical
119.4
C15–C16–H16
Torsion angles (˚)
O1–C9–C10–C11
O1–C9–C16–C15
C8–C1–C2–C3
C1–C2–C3–C6
C1–C2–C3–C4
C2–C3–C6–C7
C4–C3–C6–C7
C2–C3–C6–C5
C4–C3–C6–C5
C3–C6–C7–C8
C5–C6–C7–C8
C9–O1–C8–C7
C9–O1–C8–C1
C6–C7–C8–O1
C6–C7–C8–C1
C8–O1–C9–C10
C8–O1–C9–C16
C16–C9–C10–C11
C9–C10–C11–C12
C10–C11–C12–C15
C10–C11–C12–C13
C11–C12–C15–C16
C13–C12–C15–C16
C11–C12–C15–C14
C13–C12–C15–C14
C10–C9–C16–C15
C2–C1–C8–O1
ꢅ175.22(13)
175.42(12)
ꢅ1.4(2)
ꢅ176.73
176.89
ꢅ0.44
ꢅ0.10
ꢅ179.77
0.50
Parameters
Experimental
Theoretical
Bond lengths (Å)
N1–C4
N2–C5
N3–C13
N4–C14
O1–C8
O1–C9
C1–C2
C1–C8
C2–C3
C3–C6
C3–C4
C5–C6
C6–C7
C7–C8
C9–C10
C9–C16
C10–C11
C11–C12
C12–C15
C12–C13
C14–C15
C15–C16
C1–H1
C2–H2
C7–H7
C10–H10
C11–H11
C16–H16
1.4(2)
1.140(19)
1.144(2)
1.149(2)
1.140(19)
1.381(16)
1.386(16)
1.382(2)
1.388(2)
1.392(2)
1.408(19)
1.441(19)
1.444(2)
1.386(18)
1.384(19)
1.380(19)
1.386(19)
1.389(2)
1.392(2)
1.397(18)
1.448(2)
1.446(19)
1.395(19)
0.930
1.154
1.154
1.154
1.154
1.376
1.374
1.387
1.395
1.400
1.412
1.428
1.430
1.396
1.390
1.395
1.392
1.385
1.401
1.411
1.427
1.430
1.398
1.082
1.082
1.081
1.082
1.082
1.081
ꢅ176.61(12)
0.11(19)
178.08(12)
ꢅ176.82(13)
1.15(19)
ꢅ1.47(19)
175.48(12)
ꢅ134.49(13)
51.97(18)
ꢅ172.13(11)
1.4(2)
ꢅ179.82
ꢅ179.71
ꢅ0.04
ꢅ0.35
179.86
ꢅ142.11
42.16
ꢅ176.01
ꢅ0.20
ꢅ148.57
35.31
ꢅ165.22(13)
18.3(2)
1.4(2)
ꢅ0.54
ꢅ0.26
0.62
ꢅ179.44
ꢅ0.19
179.87
179.38
ꢅ0.54
0.96
ꢅ0.5(2)
ꢅ0.8(2)
176.16(14)
1.3(2)
ꢅ175.76(13)
ꢅ179.35(13)
3.61(19)
ꢅ0.9(2)
173.13(12)
ꢅ0.4(2)
176.13
ꢅ0.58
179.82
0.930
0.930
0.930
0.930
C12–C15–C16–C9
C14–C15–C16–C9
Å: angstrom unit; ꢀ: degree.
ꢅ179.79(12)
0.930
Bond angles (˚)
N1–C4–C3
N2–C5–C6
N3–C13–C12
N4–C14–C15
O1–C8–C7
O1–C8–C1
C8–O1–C9
C2–C1–C8
C1–C2–C3
C2–C3–C6
C2–C3–C4
C6–C3–C4
C7–C6–C3
C7–C6–C5
C3–C6–C5
C8–C7–C6
C7–C8–C1
C10–C9–C16
C10–C9–O1
C16–C9–O1
C9–C10–C11
C10–C11–C12
C11–C12–C15
C11–C12–C13
C15–C12–C13
C16–C15–C12
C16–C15–C14
C12–C15–C14
C9–C16–C15
C2–C1–H1
C8–C1–H1
C1–C2–H2
C3–C2–H2
C8–C7–H7
C6–C7–H7
C9–C10–H10
C11–C10–H10
C10–C11–H11
C12–C11–H11
C9–C16–H16
179.41(17)
177.34(17)
177.07(18)
178.73(16)
115.42(12)
122.34(12)
121.21(10)
119.54(13)
119.85(13)
119.79(12)
120.27(13)
119.91(13)
120.38(12)
119.30(12)
120.24(12)
118.49(12)
121.92(12)
120.72(12)
115.31(12)
123.88(11)
119.98(13)
120.57(12)
118.76(12)
122.09(12)
119.09(13)
120.85(12)
120.50(12)
118.64(12)
119.10(12)
120.2
178.57
178.63
178.51
178.50
116.25
122.76
121.87
119.36
120.97
119.06
119.61
121.32
119.90
119.00
121.08
119.83
120.84
120.72
116.30
122.85
119.74
120.78
118.98
119.67
121.33
120.19
118.74
121.05
119.56
120.1
2247 cmꢅ1 for 6-311G(d,p)[60] as spectral and theoretical val-
ues, respectively.
C–O stretching vibration, which is remarkable with
another high-intensity value, was observed at 1278 cmꢅ1
experimentally, at 1261 cmꢅ1 theoretically as pure mode
(13%) and at 1249 cmꢅ1 experimentally, at 1231 cmꢅ1 theor-
etically as mixed mode (11%). This band was assigned at
1259, 1224 cmꢅ1 with 6-311G(d)þ basis set and 1266,
1232 cmꢅ1 with 6-31G(d) basis set in similar studies.[15,61]
The aromatic group carbon-carbon stretching vibrations of
the compound were recorded in pure mode (in the range of
28–12%) according to PED analysis at 1593, 1578, 1542,
1287, 1278, 1214 cmꢅ1 theoretically, whereas these vibrations
were observed at the range of 1587–1202 cmꢅ1 in FT-IR
spectrum. These peak values have been recorded at
1650–1200 cmꢅ1, which is the expected frequency range for
carbon-carbon stretching vibrations specified.[62] The
C–C–C in-plane bending vibrations with the other vibration
modes were observed as mixed at 1181, 742, 610, 530, 481,
170, 163, 114 cmꢅ1 and at 721-622, 549, 457, 432, 403 cmꢅ1
as pure mode (in the range of 17–-10%). In addition, the
other in-plane, out-of-plane bending and torsion modes of
the compound are shown experimentally and theoretically in
Table 4.
120.2
120.1
120.1
120.8
120.8
120.0
120.0
119.7
120.4
119.9
119.0
119.5
120.6
119.0
121.2
120.0
It has been observed that the experimental and theoretical
values observed in the vibrational spectral characterization
process of the compound are consistent with each other and
similar studies in the literature. Correlation graph for spec-
tral and theoretical vibration frequencies is given with S.4 in
the Supplemental Material section and R2 value is 0.9992.
119.7
120.4
119.1
120.9
(continued)

6
S. ERYILMAZ ET AL.
Table 4. Comparison of the observed and calculated vibrational frequencies of the 4,40-oxydiphthalonitrile compound.
Vib. Modes
Assignmentsa
Experimentalfrequencies (cmꢅ1
)
Calculated frequencies (cmꢅ1
)
I (km/mol)
v1
v2
v3
v4
v5
v6
v7
v8
tCH(99)sym.
tCH(90)sym.
tCH(48)sym
tCH(58)sym
tCH(52)
3102
3073
–
–
–
3038
2232
–
–
–
–
1587
–
1568
–
1483
1418
–
1336
1308
1278
–
1249
1202
1194
1165
1151
–
3113
3111
3109
3107
3098
3096
2274
2273
2269
2268
1593
1578
1550
1542
1472
1468
1399
1388
1287
1278
1261
1248
1231
1214
1181
1178
1152
1135
1083
1071
959
953
951
911
882
876
834
827
742
734
728
721
710
689
639
622
615
610
549
537
536
530
481
457
439
432
418
403
382
378
349
272
249
248
170
163
140
132
114
111
93
88
38
23
13
1.73
0.30
1.38
0.51
0.87
2.14
2.75
3.49
asym
tCH(60)
asym.
tCꢃN(79)þ tCC(10)
tCꢃN(78)þ tCC(10)
tCꢃN(77)þ tCC(10)
tCꢃN(77)þ tCC(10)
tCC(14)
v9
10.04
17.86
7.48
215.62
88.36
13.23
33.36
273.52
57.04
3.58
164.43
46.85
257.17
3.33
299.47
5.79
38.54
21.15
61.34
3.03
30.51
4.72
67.71
3.03
2.97
v10
v11
v12
v13
v14
v15
v16
v17
v18
v19
v20
v21
v22
v23
v24
v25
v26
v27
v28
v29
v30
v31
v32
v33
v34
v35
v36
v37
v38
v39
v40
v41
v42
v43
v44
v45
v46
v47
v48
v49
v50
v51
v52
v53
v54
v55
v56
v57
v58
v59
v60
v61
v62
v63
v64
v65
v66
v67
v68
v69
v70
v71
v72
v73
v74
v75
tCC(14)
tCC(27)þdCCC(10)
tCC(28)
dHCC(19)
dHCC(19)
tCC(17)þdHCC(11)
tCC(18)þdHCC(10)
tCC(20)
tCC(23)
tCO (13)
dHCC(16)
tCC(15)þ tCO (11)þdHCC(10)
tCC(12)
tCC(22)þ dHCC(21)þ dCCC(12)
tCC(21)þ dHCC(17)
dHCC(13)
tCC(10)þ dHCC(10)
dHCC(13)
1092
–
dHCC(15)
tCC(12)þ dHCC(11)
sCCCC(16)þ sHCCC(44)
sCCCC(10)þ sHCCC(44)
sHCCC(30)
979
967
926
905
851
–
–
–
756
–
–
720
–
–
641
625
612
–
554
–
528
–
488
468
449
–
412
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
7.23
sHCCC(65)
11.18
16.33
20.67
34.04
8.54
0.25
1.82
0.65
1.01
0.56
0.82
0.54
12.01
1.79
sHCCC(60)þ sCCCC(12)
sHCCC(45)
sHCCC(40)
tCC(13)þ dCCC(13)
cCCCC(11)
cCCCC(12)
dCCC(11)
dCCC(15)
dCCC(16)
dCCC(13)
dCCC(11)
cOCCC(14)
dCCC(13)þ dNCC(10)
dCCC(10)
0.49
sNCCC(28)þcCCCC(15)
sNCCC(36)þcCCCC(20)
dNCC(16)þ dCCC(15)
dNCC(17)þ dCCC(10)
dCCC(17)
11.85
17.94
5.84
0.47
1.09
7.98
1.99
1.54
0.07
1.18
1.32
4.47
1.32
2.57
2.45
7.77
11.24
0.91
0.31
1.68
1.49
2.35
1.92
3.37
1.09
3.44
sCCCC(18)þcOCCC(14)
dCCC(13)
dCCC(14)
dCCC(10)
sNCCC(23)þ sCCCC(12)
sNCCC(24)þ sCCCC(11)
dOCC(23)
dCCO(14)
sNCCC(23)þcCCCC(22)þ cOCCC(12)
sNCCC(23)þcCCCC(22)þ cOCCC(12)
dCOC(11)þ dCCC(13)þ dNCC(16)
dCCC(13)þ dNCC(15)
sNCCC(12)þcCCCC(24)
cCCCC(33)þsCCCC(11)þ sNCCC(16)
dNCC(16)þ dCCC(22)
dNCC(21)þ dCCC(26)
sCCCC(15)þcCCCC(15)
sCCCC(28)þ cCCCC(17)
dCOC(23)þsCCCC(13)þcCCOC(12)
dCOC(10)þsCCOC(47)
sCCOC(57)
Calculated vibrational frequencies were obtained with Becke, three-parameter, Lee-Yang-Parr/6-311G(d,p) level of theory.
aPED: Potential energy distribution, less than 10% are not shown.I: intensity (km/mol). Vibrational modes: ꢀ: stretching (sym: symmetric; asym: asymmetric); d: in
plane bending; c: out of plane bending; s: torsion.

SPECTROSCOPY LETTERS
7
1
the remote field. The spectral H-NMR chemical shift values
were recorded in the range of 8.22–7.68 ppm, whereas theor-
etical ones 6.76–6.04 ppm, 8.17-–7.34 ppm, 6.76–6.05 ppm
respect to CSGT, GIAO, and IGAIM methods, respectively.
The aromatic protons of 4,40-oxydiphthalonitrile, H11 and
H2 were assignment as a singlet at 8.22, 8.20 ppm, H7 and
H10 at 8.03 ppm doublet, H1 and H16 at 7.70, 7.68 ppm
1
doublet in the spectrum. The H chemical shift values of the
compound both spectral and also theoretical are consistent
with the range of 8.5–6 ppm which observed aromatic pro-
ton NMR signals.
The correlation graphs, correlation coefficients and qual-
ity of the linear relationship were used to analyze the har-
mony between spectral and theoretical approaches. As can
be seen from S.5 to S.10 (in the section of Supplemental
Material), for the 13C-NMR values, CSGT and IGAIM meth-
ods gave shift values very close to each other with 0.9882
correlation coefficient value, whereas the GIAO method
showed a more consistent result with spectral results with 0.
9924 correlation coefficient value. Similarly, for the 1H-
NMR chemical shift values, the correlation coefficient values
of the CSGT and IGAIM methods are found to be 0.8310, 0.
8306, and 0.9770 for the GIAO method. According to the
results of this comparison; it is seen that CSGT and IGAIM
methods provide a close approximation to the GIAO
method with respect to carbon NMR spectral values of 4,40-
oxydiphthalonitrile, but GIAO method for proton NMR val-
ues gives more consistent results than others.
Figure 3. Experimental Fourier transform-infrared spectrum and simulated
spectrum, which plotted on the transmittance (%) against the wavenumbers
(cmꢅ1) for the 4,40-oxydiphthalonitrile compound in the range 4000–400 cmꢅ1
.
Nuclear magnetic resonance spectral analysis
1
The 13C-Attached proton test (APT), H-NMR spectrums of
the 4,40-oxydiphthalonitrile compound shown in Figures 4
and 5 were examined and compared with the results
obtained the theoretical approaches, the finding of this ana-
lysis are tabulated in Table 5.
The spectral 13C-NMR (APT) chemical shift values of the
4,40-oxydiphthalonitrile compound were recorded in the
range 158.87–111.06 ppm, whereas theoretical values
163.43–114.14 ppm, 168.03–117.24 ppm, 163.45–114.16 ppm
with respect to CSGT, GIAO, and IGAIM approaches,
respectively. sp2 hybridized C8 and C9 atoms which have
attached to the oxygen atom with electronegative character
have the highest chemical shift value by virtue of showing
absorption in downfield. The chemical shift values of aro-
matic carbon atoms are recorded in generally a wide range
such as 100–150 ppm,[63] when these values are examined
for the compound, it has been determined that chemical
shift values of the C2 and C11 atoms have higher than the
others due to mesomeric effects. The chemical shift values
of these atoms were recorded 137.03 ppm as experimental,
141.851, 141.968 ppm as to CSGT, 145.454, 145.369 ppm as
to GIAO and 141.858, 141.973 ppm as to IGAIM methods.
C4, C5, C13, and C14 atoms signals were observed at
Ultraviolet-visible spectral and frontier molecular
orbitals analysis
UV-Vis spectral analysis of the 4,40-oxydiphthalonitrile com-
pound was recorded in the different solvents such as chloro-
form (CHCl3), tetrahydrofuran (THF), dichloromethane
(DCM), ethanol (EtOH), and methanol (MeOH) within
220–450 nm range. At the same time, some UV-Vis parame-
ters of the compound were investigated at the theoretical
level with TD-DFT/B3LYP/6-311G(d,p) in both the gaseous
phase and the before mentioned solvents media. The spec-
tral and theoretical absorption wavelengths (nm), excitation
energies (eV), oscillator strengths (f), and the major contri-
bution to probable orbital transitions are tabulated in Table
6. The obtained electronic absorption spectrum of the com-
pound in the different solvents is given in Figure 6. The
observed absorption wavelengths values in spectra are 259,
291, 299 nm in CHCl3, 258, 293, 301 nm in THF, 259, 292,
301 nm in DCM, 259, 291, 299 nm in EtOH, 259, 292,
301 nm in MeOH solvent. The theoretical wavelengths cor-
responding to the maximum of these values and the contri-
bution rates of the HOMO!LUMO transitions estimated
for the first excited states are 296.50 nm with (72%) in
CHCl3, 297.07 nm with (75%) in THF, 297.36 nm with
(78%) in DCM, 297.90 nm with (79%) in EtOH, 297.87 nm
116.14,
115.71,
ppm,
and
at
the
range
of
122.299–117.267 ppm according to spectral and based on the
theoretical analysis results, respectively. As it is well known,
the nitrile group sp hybridized carbon atoms (CꢃN) gener-
ally have such as 113–120 ppm a narrow range of chemical
shift values,[64] it can be said that these values obtained for
4,40-oxydiphthalonitrile compound are in accordance with
the literature. Also, the stated chemical shift values were
recorded as 122.1, 119.6 ppm,[49] 114.70, 116.73 ppm[22] in
the other phthalonitrile studies. From the remaining sp2
hybridized carbon atoms (C–CꢃN), the chemical shift val- with (78%) in MeOH. These transitions with maximum
ues of C6 and C15 were observed at 117.54 ppm with wavelength and low excitation energies can said to be
ꢇ
respect to spectral results, whereas C3 and C12 signal at related to n!p transitions due to the presence of cyano
111.06 ppm a lower value than this owing to the effect of groups. It can be said that other absorption wavelength

8
S. ERYILMAZ ET AL.
13
Figure 4. C APT spectrum of the 4,40-oxydiphthalonitrile compound in DMSO. Chemical shift values have expressed as ppm. In the APT spectrum of the com-
pound, methine group carbons; positive, quaternary group carbons; negative signal. APT: attached proton test; DMSO: dimethyl sulfoxide; ppm: parts per million.
1
Figure 5. H-Nuclear magnetic resonance spectrum of the 4,40-oxydiphthalonitrile compound in DMSO. Chemical shift values have expressed as ppm. DMSO:
dimethyl sulfoxide; ppm: parts per million.
ꢇ
values are due to p!p electronic transitions related to the of the title compound do not exhibit a noticeable change, it
aromatic group. In this analysis process, different solvents can be interpreted that there is not any chemical interaction
were used, such as CHCl3 as a non-polar solvent having low with the solvent.
Highest Occupied Molecular Orbital (HOMO) and
Lowest Unoccupied Molecular Orbital (LUMO) energy val-
ues, which are defined as frontier molecular orbitals (FMOs)
energies, are quite important in the process of determining
the UV-Vis spectral characterization of molecules. In add-
dielectric constant, EtOH and MeOH as protic polar sol-
vents participating in the hydrogen bond having high dielec-
tric constant, THF, and DCM as aprotic polar solvents
nonparticipating to hydrogen bond due to the lack of O-H
or N-H bond.
When different solvents are used in UV-Vis absorption ition, charge transfer between the HOMO-LUMO levels
spectral analyses of molecular structures, it is generally plays an active role in intermolecular and intramolecular
expected that there will be some changes in the wavelength interactions such as dimerization and polymerization. The
values of observed absorption or in intensity. However, the energy difference between these levels, called "band gap", has
fact that the spectral and theoretical absorption bands values examined for 4,40-oxydiphthalonitrile compound in the

SPECTROSCOPY LETTERS
9
Table 5. Experimental and theoretical 13C and 1H isotropic chemical shift val-
with different polarities, and the results are presented in
Table 7.
ues of the 4,40-oxydiphthalonitrile compound.
Atoms
Experimental (ppm)
CSGT (ppm)
GIAO (ppm)
IGAIM (ppm)
According to the obtained results; the total energy, ion-
ization potential, electron affinity, electronegativity, and elec-
trophilicity index values of the 4,40-oxydiphthalonitrile
compound have decreased with increasing polarity of sol-
vents, but dipole moment and global chemical softness val-
ues increased. In solvent media with higher dielectric
constant or polarity, the compound has a character less elec-
tronegative and less hard with increasing dielectric constant
and it may be considered that the molecule is more reactive
and therefore the charge transfer is more likely in the
molecular structure.
C1
C2
C3
C4
C5
C6
C7
C8
125.15
137.03
111.06
116.14
115.71
117.54
125.20
158.87
158.87
125.20
137.03
111.06
116.14
115.71
117.54
125.15
7.70
124.831
141.851
114.794
117.543
117.267
121.391
130.379
162.864
163.436
128.361
141.968
114.149
117.587
117.226
120.867
124.505
6.334
129.430
145.454
117.886
122.299
122.069
124.682
135.262
167.638
168.030
132.975
145.769
117.245
122.380
121.957
124.124
129.451
7.469
124.841
141.858
114.809
117.553
117.277
121.406
130.387
162.885
163.456
128.367
141.973
114.164
117.597
117.236
120.884
124.517
6.341
C9
C10
C11
C12
C13
C14
C15
C16
H1
Molecular electrostatic potential analysis
H2
8.20
6.683
8.068
6.686
H7
8.03
8.03
8.22
7.68
6.456
6.587
6.766
6.047
7.928
7.877
8.173
7.344
6.459
6.587
6.767
6.057
The molecular electrostatic potential map (MEP) was com-
posed at the B3LYP/6-311G(d,p) level to examine the charge
distribution of the 4,4’-oxydiphthalonitrile compound. MEP
visuals are very helpful in determining the electron charge
densities of the molecular structures, therefore, their reactive
sites, and also possible intermolecular interactions.[70–72] In
these maps, the exchange of electron density on the whole
molecule is visualized with start from red, towards yellow,
green and blue color tones. As can be seen at S.11 (in the
section of Supplemental Material), the regions (surrounded
by red and yellow tones) having a more negative electro-
static potential than the others are around the nitrogen
atoms N1, N2, N3, and N4 with values -0.022, -0.0016, -0.
014, -0.0019 a.u., respectively, whereas areas where the
hydrogen atoms are condensed (surrounded by blue tones)
have more positive electrostatic potential values. It is appar-
ent from this analysis that the most susceptible part of the
4,40-oxydiphthalonitrile compound to the electrophilic attack
is around the nitrogen atoms, whereas for the nucleophilic
attack it is considered to be around the hydrogen atoms. In
addition, the MEP image corroborates the presence of the
C—HꢄꢄꢄN type intermolecular hydrogen bonds interaction of
the compound described in the section of description of the
single-crystal structure.
H10
H11
H16
Theoretical values were obtained with Becke, three-parameter, Lee-Yang-Parr/
6-311G(d,p) level of theory.
ppm: parts per million; CSGT: continuous set of gauge transformations; GIAO:
gauge-independent atomic orbital; IGAIM: individual gauges for atoms in
molecules approaches. Chemical shift values of the carbon and hydrogen
atoms are based on the atom numbering given in Figure 1.
gaseous phase, and it has been established as DE ¼EHOMO
-
ELUMO¼4.67 eV. For similar phthalonitrile derivative mol-
ecule groups in the other papers, this energy range was cal-
culated as 4.35 eV[22] and 4.32 eV,[16] with 6-31G(d) as
3.04 eV[15] with 6-311 þ G(d) basis sets. According to these
results, within the compared phthalonitrile groups, the 4,40-
oxydiphthalonitrile compound has exhibited higher kinetic
stability and lower chemical reactivity character with large
DE value. Figure 7 shows diagrams of the molecular orbitals
which are more likely to interact and the energy gaps
between them.
Besides, FMOs energies play a decisive role in examining
the chemical reactivity or stability properties of molecular
structures at the theoretical level. Ionization potential (I)
and electron affinity (A) concepts are defined by the equa-
tions I¼-EHOMO and A¼-ELUMO
,
as suggested by
Koopmans,[65] also express the energy changes observed at
the electron donate-accept processes of the molecular sys-
tem. Other reactivity parameters that help to obtain infor-
mation about the formation of chemical bonds or possible
intramolecular charge transfers are known as electronegativ-
ity (v), global chemical hardness-softness (g, S), electronic
chemical potential (l), and electrophilicity index (x) values.
These parameters which are named as global reactivity
descriptors give information about global reactivity behav-
iors over the whole molecular structure and can be calcu-
lated with I and A values; v ¼ (I þ A)/2, g ¼ (I-A)/2, S¼1/2g,
l¼ -(I þ A)/2 and x¼ l2/2g,[66–69] respectively. The total
energy, dipole moment, frontier molecular orbital energies,
and some global reactivity descriptors for the 4,40-oxydiph-
thalonitrile compound were calculated at TD-DFT/B3LYP/6-
Non-linear optical properties analysis
In order to investigate whether or not the 4,40-oxydiphthalo-
nitrile compound having non-linear optical (NLO) material
properties; the dipole moment, polarizability, and first-order
hyperpolarizability values were examined theoretically at the
B3LYP/6-311G (d,p) level. These parameters have high val-
ues especially in molecular structures with conjugated p-
electrons, and as a result of possible occurring intramolecu-
lar charge transfer over these groups.[73] It is known that
molecules exhibiting high dipole moment and polarizability
also carry the potential to become NLO materials. Organic
NLO materials are used in many optoelectronic system
designs in a wide range of fields ranging from optical data
processing and storage areas to organic light emitting diode
(OLED) applications in parallel to today’s developing
311G(d,p) level in gaseous phase and solvent environments technology.[74–76]

10
S. ERYILMAZ ET AL.
Table 6. Experimental and calculated ultraviolet-visible spectral parameters 4,40-oxydiphthalonitrile compound.
Experimental
Theoretical
Excitation
Oscillator
Probable
Media
wavelength k (nm)
wavelength k (nm)
energy (eV)
strength f
Major contributions
transitions
ꢇ
Gaseous
265.73
4.665
0.0024
HOMO!LUMO þ2 (39%)
HOMO-3!LUMO (13%)
HOMO-2!LUMO (11%)
HOMO!LUMO þ1 (72%)
HOMO!LUMO (16%)
p!p
ꢇ
ꢇ
294.52
298.10
265.60
4.209
4.159
4.6681
0.2368
0.2307
0.0066
n!p
n!p
p!p
HOMO!LUMO (79%)
HOMO!LUMO þ1 (15%)
HOMO!LUMO þ2 (34%)
HOMO-3!LUMO (13%)
HOMO-2!LUMO þ1 (11%)
HOMO!LUMO þ1 (65%)
HOMO!LUMO (24%)
ꢇ
CHCl3
259
ꢇ
ꢇ
291
299
258
293.67
296.50
265.62
4.2219
4.1815
4.6677
0.2754
0.2135
0.0048
n!p
n!p
HOMO!LUMO (72%)
HOMO!LUMO þ1 (21%)
HOMO!LUMO þ2 (37%)
HOMO-3!LUMO (13%)
HOMO-2!LUMO þ1 (11%)
HOMO!LUMO þ1 (69%)
HOMO!LUMO (20%)
THF
ꢇ
p!p
ꢇ
ꢇ
293
301
259
293.98
297.07
265.65
4.2175
4.1736
4.6671
0.2579
0.2237
0.0043
n!p
n!p
p!p
HOMO!LUMO (75%)
HOMO!LUMO þ1 (18%)
HOMO!LUMO þ2 (38%)
HOMO-3!LUMO (13%)
HOMO-2!LUMO þ1 (11%)
HOMO!LUMO þ1 (71%)
HOMO!LUMO (18%)
ꢇ
DCM
EtOH
MeOH
ꢇ
ꢇ
292
301
259
294.19
297.36
265.70
4.2145
4.1695
4.1620
0.2491
0.2368
0.2339
n!p
n!p
p!p
HOMO!LUMO (78%)
HOMO!LUMO þ1 (16%)
HOMO!LUMO þ2 (39%)
HOMO-3!LUMO (13%)
HOMO-2!LUMO þ1 (11%)
HOMO!LUMO þ1 (72%)
HOMO!LUMO (17%)
ꢇ
ꢇ
ꢇ
291
299
259
294.43
297.90
265.69
4.2109
4.1620
4.6664
0.2395
0.0029
0.0027
n!p
n!p
p!p
HOMO!LUMO (79%)
HOMO!LUMO þ1 (15%)
HOMO!LUMO þ2 (39%)
HOMO-3!LUMO (13%)
HOMO-2!LUMO þ1 (11%)
HOMO!LUMO þ1 (71%)
HOMO!LUMO (18%)
ꢇ
ꢇ
ꢇ
292
301
294.37
297.87
4.2118
4.1623
0.2413
0.2248
n!p
n!p
HOMO!LUMO (78%)
HOMO!LUMO þ1 (16%)
Calculated parameters were obtained with Becke, three-parameter, Lee-Yang-Parr/6-311G(d,p) level of theory.
k: Wavelength (nanometer); eV: energy unit (electron volt); HOMO: highest occupied molecular orbital; LUMO: lowest unoccupied molecular orbital; CHCl3: chloro-
form; THF: tetrahydrofuran; DCM: dichloromethane; EtOH: ethanol; MeOH: methanol.
equations and their numerical values are tabulated in
Table 8;[77,78]
ꢀ
ꢁ
1=2
ltot ¼ l2x þ l2y þ l2z
(2)
(3)
< a >¼ axx þ ayyþazz =3
ð
Þ
2
2
btot ¼ ½ðbxxx þ bxyy þ bxzzÞ þ ðbyyy þ byzz þ byxx
Þ
(4)
2 1=2
þ ðbzzz þ bzxx þ bzyyÞ ꢈ
The calculated ltot, <a>, btot values are 6.2084 D,
30.3270 ꢁ 10ꢅ24 esu, and 3391.49 x10ꢅ33 esu, respectively, as
seen in Table 8. In order to determine the effect of the
potential NLO character of compound 4,40-oxydiphthaloni-
trile, the values of total dipole moment, mean polarizability
and first-order hyperpolarizability have been calculated for
the same theoretical level for the urea molecule, which is
accepted as a threshold value in such analysis, and the
Figure 6. Ultraviolet-visible spectrum of the 4,40-oxydiphthalonitrile compound
at the different solvents in the range 220–450 nm. nm: nanometer wavelength
scale. The used solvents are MeOH-methanol; EtOH: ethanol; DCM: dichlorome-
thane; CHCl3: chloroform; THF: tetrahydrofuran.
The total electric dipole moment, ltot, mean polariz-
ability, <a>, total first-order hyperpolarizability, btot, val-
ues parameters were calculated using the following obtained results are 3.8872 D, 5.0098 ꢁ 10ꢅ24 esu and

SPECTROSCOPY LETTERS
11
621.3132 ꢁ 10ꢅ33esu. According to these compared values, Thermodynamic properties analysis
ltot, of the compound 4,40-oxydiphthalonitrile is 1.7 times,
<a> is 7.30 times, and btot is 5.69 times higher than urea
molecule. In paper realized by Anbarasan et al.,[79] which
has structural similarities with the title compound in the lit-
erature, the NLO behavior of 4-(phenylthio) phthalonitrile, a
phthalonitrile derivative, was investigated. The first-order
hyperpolarizability value of this compound calculated with
the basis set of 6-311 þþG(d,p) is 47.0841 ꢁ 10ꢅ33 esu (5.45
a.u.) and 4,40-oxydiphthalonitrile has a higher value than
that compound. These results show that the compound sub-
ject to this study exhibits a character that may be evaluated
by researchers in NLO material studies.
Characteristic thermodynamic parameters such as heat cap-
acity, Cp0;m, entropy, Sm0 , and enthalpy change, DHm0 , for the
4,40-oxydiphthalonitrile compound were examined at tem-
perature values ranging from 100 K to 800 K and at 1 atm
pressure with B3LYP/6-311G(d,p) method. The increased
vibration densities of the molecular structures with raising
temperature have caused the values of heat capacity,
entropy, and enthalpy change parameters to change in pro-
portion to the increasing temperature. Correlation graph
showing the change of thermodynamic parameters of the
4,40-oxydiphthalonitrile compound with temperature is
shown in Figure 8.
The results which show the variation of the mentioned
parameters with the temperature are tabulated in Table 9,
and the correlation equations in which each parameter is
represented as a function of temperature and corresponding
fitting factors (R2) are as follows:
0
ꢅ4
2
2
ð
Þ
ð Þ
Cðp;m T ¼ 5:14661 þ 0:23354Tꢅ1:19141:10 T R ¼ 0:9997
Þ
S0m T ¼ 82:87945 þ 0:13559Tꢅ3:64371:10 T R ¼ 0:9618
ꢅ5
ꢅ5
2
2
ð
Þ
ð Þ
DHm0 T ¼ ꢅ1:93733 þ 0:02771T þ 6:2996:10 T R ¼ 0:9995
2
2
ð
Þ
ð Þ
Conclusions
In this paper, we present the results of both spectral and
theoretical analyses used to determine the structural proper-
ties of a compound starting from the synthesis process. The
single crystal and molecular structure, characteristic of the
functional groups, the interaction with the molecule envir-
onment and carbon skeleton, analysis of electronic transi-
tions were investigated by using XRD technique and FT-IR,
NMR, UV-Vis spectral methods for the title compound.
Theoretical analyses were performed with the DFT/B3LYP/
6-311G(d,p) basis set and the experimental data were com-
pared with those calculated. The harmony between these
values was examined with correlation graphs and correlation
coefficients and satisfactory results were obtained. The calcu-
lated correlation values for spectral and theoretical results
have given us an idea of the reliability of the results
obtained from the next steps of the theoretical studies. Band
gap value was calculated as 4.67 eV with FMO analysis and
Figure 7. Molecular orbital diagrams and energy levels of the 4,40-oxydiphtha-
lonitrile compound. HOMO: highest occupied molecular orbital; LUMO: lowest
unoccupied molecular orbital energy values; eV: energy unit (electron volt).
Table 7. Total energy, dipole moment and ionization potential, electron affinity, electronegativity, global chemical hardness, global chemical softness, electronic
chemical potential, electrophilicity index values in different media for the 4,4’-oxydiphthalonitrile compound.
Gaseous (e ¼ 1)
CHCl3 (e ¼ 4.71)
THF (e ¼ 7.42)
DCM (e ¼ 8.93)
EtOH (e ¼ 24.85)
MeOH (e ¼ 32.61)
ETOTAL
lDipole
EHOMO
ELUMO
ꢅ907.558207
ꢅ907.5510
7.7544
ꢅ7.402
ꢅ2.698
7.402
ꢅ907.5537
7.9557
ꢅ7.352
ꢅ2.659
7.352
ꢅ907.5546
8.0169
ꢅ7.337
ꢅ2.647
7.337
ꢅ907.5571
8.2175
ꢅ7.287
ꢅ2.609
7.287
ꢅ907.5574
8.2452
ꢅ7.281
ꢅ2.604
7.281
8.2974
ꢅ7.268
ꢅ2.594
7.268
I
A
v
g
S
l
x
2.594
4.931
2.336
0.21398
ꢅ4.93155
5.20406
2.698
5.050
2.351
0.21260
ꢅ5.05033
5.42272
2.659
5.005
2.346
0.21308
ꢅ5.00584
5.33964
2.647
4.992
2.344
0.21324
ꢅ4.99237
5.31495
2.609
4.948
2.338
0.21376
ꢅ4.94883
5.23541
2.604
4.942
2.338
0.21384
ꢅ4.94285
5.22458
ETOTAL:Total Energy (a.u.-atomic unit); lDipole: dipole moment (Debye); EHOMO: highest occupied molecular orbital energy value; LUMO: lowest unoccupied molecu-
lar orbital energy value; eV: energy unit (electron volt); I: ionization potential (eV); A: electron affinity (eV); v: electronegativity (eV); g: global chemical hardness
(eV); S: global chemical softness (eVꢅ1); l: electronic chemical potential (eV); x: electrophilicity index (eV).

12
S. ERYILMAZ ET AL.
Table 8. Components of the electric dipole moment and total dipole moment
(Debye), components of the polarizability and mean polarizability (ꢁ10ꢅ24esu),
components of the first-order hyperpolarizability and total first-order hyperpo-
larizability (ꢁ10ꢅ33esu) values for the 4,40-oxydiphthalonitrile compound.
hyperpolarizability of the compound were theoretically cal-
culated and compared with the values of the urea molecule.
The hyperpolarizability value of the compound is 5.69 times
greater than the threshold value, indicating that it has the
potential to become an NLO material. Some thermodynamic
parameters at different temperature values were examined
and a change parallel to the temperature increase was
observed. Namely, the results obtained from the spectro-
scopic analysis of the compound were compared with simi-
lar molecular structures containing other phthalonitrile
moiety and evaluated in the relevant portions of the text.
The theoretical analyses established with the selected basis
set and method gave satisfactory results with experimental
findings. Phthalocyanines have a delocalized p electron sys-
tem, and role as electrochemical materials in high-tech sys-
tems due to their interesting photophysical and good-optical
properties such as electron transfer ability.
First-order
Electric dipole
moment (Debye)
B3LYP /
6-311G(d.p)
hyperpolarizability
B3LYP /
6-311G(d.p)
(ꢁ10ꢅ33esu)
lx
ly
lz
ltot
1.7730
ꢅ4.9533
ꢅ3.2963
6.2084
bxxx
bxxy
bxyy
byyy
bxxz
3121.3111
2797.9150
ꢅ511.3180
ꢅ744.6925
ꢅ731.0744
Polarizability
(ꢁ10ꢅ24esu)
axx
47.2411
ꢅ0.8080
25.7466
ꢅ2.7644
ꢅ0.2198
17.9932
30.3270
bxyz
byyz
bxzz
byzz
bzzz
btot
179.7435
ꢅ116.8880
ꢅ8.0790
axy
ayy
axz
ayz
azz
˂; a >
ꢅ200.8260
ꢅ292.5835
3391.4900
esu: electrostatic unit.
Phthalonitrile and its derivatives pioneer the synthesis of
phthalocyanines which cannot be found naturally, and thus
obtained by synthetic processes. Researchers maintain to
work on the synthesis of new phthalocyanines with free
metal, metallophthalocyanines, or bridged network poly-
meric functional groups by functioning with compounds of
different substituents groups and phthalonitrile moieties. For
this reason, each new phthalonitrile-derived compound
exhibiting different structural properties will lead to the
acquisition of new phthalocyanine macro-molecules.
Furthermore, the use of 4,40-oxydiphthalonitrile as the raw
material in the patented synthesis process which of 4,40-oxy-
diphthalic acid and 4,40-oxydiphthalic dianhydride com-
pounds,[80] makes it valuable to clarify the structural
properties of the title compound. The findings in this paper
obtained for 4,40-oxydiphthalonitrile compound will be help-
ful for other phthalonitrile and substituted phthalonitrile or
similar compounds to be used to obtain phthalocyanines
from important macrocyclic groups.
Figure 8. Correlation graph of the some thermodynamic parameters of 4,40-
oxydiphthalonitrile compound in the range of 100–800 K. K: Temperature
0
(Kelvin); Cp,m0: heat capacity; Sm : entropy; DHm0 : enthalpy change.
TABLE 9. Some thermodynamic parameters of the 4,40-oxydiphthaloni-
trile compound.
Disclosure statement
T (K)
Cp0;m
Sm0
DHm0
No potential conflict of interest was reported by the authors.
100
200
298.15
400
500
600
700
800
27.457
46.569
64.357
79.978
92.283
102.031
109.806
116.09
90.022
116.254
122.865
130.242
138.879
148.614
159.220
170.525
1.913
5.808
11.465
19.044
27.879
37.813
48.618
60.122
Acknowledgments
The authors acknowledge Scientific and Technological Research
Application and Research Center, Sinop University, Turkey, for the use
of the Bruker D8 QUEST diffractometer.
The heat capacity, entropy, and enthalpy change parameters of the compound
in the range of 100–800 K were obtained with Becke three parameter Lee-
Yang-Parr/6-311G(d, p) level of theory.
Funding
Cp0;m
:
heat capacity ðcal:molꢅ1:Kꢅ1Þ; Sm0 : entropy ðcal:molꢅ1:Kꢅ1); DHm0 :
This work was supported by Amasya University Scientific Research
Foundation (FMB-BAP-15-140).
enthalpy change ðkcal:molꢅ1Þ. T (K): Temperature (Kelvin).
it can be said that compound has a higher kinetic stability
and a lower chemical reactivity than the other structures
which containing phthalonitrile derivative. It was deter-
mined by MEP analysis that the electron charge density of
the compound was high around the nitrogen and oxygen
atoms, and low around the hydrogen atoms. The dipole
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