Synthesis, solid state structure, Hirshfeld surface, nonlinear optics and DFT studies on novel bischalcone derivative

Article abstract of DOI:10.1016/j.molstruc.2018.12.045

Novel bischalcone derivative 1,5-diphenyl-3-(thiophen-2-yl)pentane-1,5-dione has been synthesized and single crystals were grown by slow evaporation using ethanol medium of solvent. The synthesized molecule has been characterized using single crystal X-ra

Full text of DOI:10.1016/j.molstruc.2018.12.045

Accepted Manuscript
Synthesis, solid state structure, Hirshfeld surface, nonlinear optics and DFT studies
on novel bischalcone derivative
S. Veeramanikandan, H. Benita Sherine, A. Dhandapani, S. Subashchandrabose
PII:
S0022-2860(18)31472-8
DOI:
https://doi.org/10.1016/j.molstruc.2018.12.045
MOLSTR 25982
Reference:
To appear in: Journal of Molecular Structure
Received Date: 29 July 2017
Revised Date: 20 October 2018
Accepted Date: 11 December 2018
Please cite this article as: S. Veeramanikandan, H.B. Sherine, A. Dhandapani, S. Subashchandrabose,
Synthesis, solid state structure, Hirshfeld surface, nonlinear optics and DFT studies on novel
bischalcone derivative, Journal of Molecular Structure (2019), doi: https://doi.org/10.1016/
j.molstruc.2018.12.045.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
dnorm
MEP
Fingerprint
Shape index

ACCEPTED MANUSCRIPT
Synthesis, solid state structure, Hirshfeld surface, nonlinear optics and DFT
studies on novel Bischalcone derivative
a
a*
b*
c
S. Veeramanikandan , H. Benita Sherine , A. Dhandapani , S. Subashchandrabose
a
b
Department of Chemistry, Periyar EVR College, Trichy-620023, Tamil Nadu, India.
Department of Chemistry, CK College of Engineering and Technology, Cuddalore-607001, Tamil Nadu,
India.
c
Centre for Functionalized Magnetic Materials (FunMagMa), Immanuel Kant Baltic Federal University-
2
36041, Kaliningrad, Russia.
Abstract
Novel bischalcone derivative 1,5-diphenyl-3-(thiophen-2-yl)pentane-1,5-dione has been
synthesized and single crystals were grown by slow evaporation using ethanol medium of
solvent. The synthesized molecule has been characterized using single crystal X-ray diffraction,
FT-IR, FT-Raman, and NMR spectral studies. The crystal structure packing and hydrogen
bonding interactions were studied using X-ray diffraction. The closer contacts in crystal lattice
and role of noncovalent interactions of synthesized compound have been studied using various
surfaces of Hirshfeld analysis. The quantum chemical density functional theory calculations were
performed with properly chosen B3LYP functional level to investigate the vibrational dynamic
picture, molecular geometries, Lewis (donor) and non-Lewis (acceptor) bond interactions and
-30
electrostatic potentials. The calculated first hyperpolarizability 12.84×10 esu shown that the
bischalcone has good nonlinear property. The energy gap of the synthesized molecule has been
analyzed from frontier molecular orbitals.
Key words: NLO, DTPD, XRD, Hirshfeld surface.
Corresponding author:
E-mail addresses : beni2@rediffmail.com(H. Benita Sherine),
dhana118msc@gmail.com (A. Dhandapani)

ACCEPTED MANUSCRIPT
1
. Introduction
Chalcones and its derivatives have wide applications in the field of nonlinear optics
NLO) [1] such as, optical switching [2], electrochemical sensing [3] and Langmuir films [4]. In
(
recent years, many researchers have been interested to synthesize organic nonlinear materials
due to their promising application in optoelectronics [5-9]. To obtain the sufficient second
harmonic generation (SHG) score in the organic molecule, it must have a non-centrosymmetric
structure, non-zero hyperpolarizability and high first order hyperpolarizabilities [10]. Chalcone
derivatives are well known for their second and third order hyperpolarizability [11, 12]. The
NLO effect in organic molecules mainly originates from donor-acceptor interactions and non-
centrosymmetry in crystals. Bischalcones have also been reported as active nonlinear materials
and possess good third order non-linearity compared with stilbazonium dyes [13].
The large molecular hyperpolarizability β is the basis for SHG response and this type of
candidates are more appreciable as NLO materials. Recent work from Chauhan et al., describes
the ferrocenyl chalcone dyes with anchoring groups act as donor type sensitizers in dye
sensitized solar cell (DSSC) [14]. The configurational isomerism and polymorphism in chalcones
influence the fluorescent properties and provide profound significance in organic light emitting
materials [15]. Chalcones having the exceptional possession including high extinction
coefficients for absorption in the ultraviolet and NLO responses [16]. Because of the substantial
importance of the nonlinear materials, a novel organic molecule 1,5-diphenyl-3-(thiophen-2-
yl)pentane-1,5-dione (DTPD) has been synthesized and characterized using spectral and X-ray
diffraction studies (XRD).In the present investigation, we report the synthesis, structural
determination and properties of a bischalcone. To investigate the molecular interactions in
crystal lattice, Hirshfeld surfaces are mapped and analyzed with its 2-dimensional fingerprint
regions. Using density functional theory (DFT) calculations, stable conformer, vibrational
assignments, donor-acceptor stabilizing interactions are studied.
2
. Synthesis of 1,5-diphenyl-3-(thiophen-2-yl)pentane-1,5-dione
Solution of acetophenone (2.4 g, 0.2 mmol) and thiophene-2-carbaldehyde (1.12g, 0.1
mmol) in absolute ethanol (30 ml) were taken in a beaker (100 ml), a catalytic quantity of
sodium hydroxide (2 pellet) was added. The reaction mixture was stirred for two hours at room
temperature. The completion of the reaction was monitored using thin layer chromatography.

ACCEPTED MANUSCRIPT
The crude product was filtered, washed with distilled water and recrystallized using absolute
ethanol. The single crystals of the synthesized compound were successfully grown by adopting
slow evaporation technique using ethanol as solvent. The defect free block like single crystals of
DTPD suitable for XRD analysis were harvested after fifteen days with the sample size of
3
0
.50×0.45×0.40 mm .
O
S
H
NaOH
+
C H OH
2
5
O
O
S
acetophenone
thiophene-2-carbaldehyde
(E)-1-phenyl-3-(thiophen-2-yl)but-2-en-1-one
The synthesis scheme of normal chalcone derivative
S
O
O
S
NaOH
2
+
C H OH
2
5
O
O
H
acetophenone
thiophene-2-carbaldehyde
1,5-diphenyl-3-(thiophen-2-yl)pentane-1,5-dione
Scheme-1. The synthesis scheme of Bischalcone derivative DTPD.
2
.1 Spectral characterization
All starting materials and solvents are of analytical grade (Merck and Sigma-Aldrich
products) were purchased and used without any further purification. Melting points were
determined in open capillary on a Guna-Mac apparatus. The FT-IR spectrum of the synthesized
-1
compound was recorded in the region 4000-400 cm migration mode using KBr pellet technique
on a Shimadzu FT-IR spectrophotometer. FT-Raman spectrum of synthesized compound was
recorded utilizing 1064 nm line of Nd:YAG laser (100 mW) as excitation wavelength within
-1
-1
spectral range 3500-50 cm . The instrument was set to 2 cm spectral resolution in back
1
scattering mode. H-NMR (400 MHz) chemical shift was recorded for approximately 0.04 m
6
solution in DMSO-d using TMS as an internal reference on a Bruker high resolution NMR.

ACCEPTED MANUSCRIPT
Single crystal X-ray diffraction was carried out at Bruker Kappa Apex II charge coupled-device
diffractometer.
3
. Computational details
The quantum chemical calculations of the DTPD were performed with Gaussian 09
program package [17] invoking geometry optimization using the Becke 3-parameter Lee-Yang-
Parr level of theory supplemented with 6-311++G(d,p) basis set. Initial geometry generated from
geometrical parameters was minimized without any constraint in the potential energy surface at
density functional theory (DFT) level. The optimized minimum structure parameters were used
in the vibrational wavenumber calculations at the DFT level to characterize all stationary points
as minima. The harmonic vibrational wavenumber calculations resulting in IR-Raman intensities
and Raman depolarization values. The vibrational modes were assigned based on potential
energy distribution analysis (PED) using VEDA4 program [18]. The Raman activities were
transformed into Raman intensities using Raint program [19] by the expression:
1
−
1 2
4
I i = 1 0
× (
ν
−
ν
)
i
×
× R A i
0
ν
i
(1)
Where I is the Raman intensity, A is the Raman scattering activities, ν is the wavenumber of
i i i
the normal modes and ν denotes the wavenumber of the excitation laser [20]. Hirshfeld surface
0
maps and fingerprint plots were generated from the crystallographic information file of DTPD
using the Crystal Explorer 3.1 [21].The non-covalent bonding–antibonding interaction can be
quantitatively described in terms of the natural bond orbital (NBO) analysis, which is expressed
(
2)
by means of the second-order perturbation interaction energy (E ) [22].
4
. Results and Discussion
4
.1 Single crystal structure
In single crystals of DTPD, asymmetric unit contains one independent molecule of
1
monoclinic system with P2 /c space group. The ORTEP plot and optimized molecular structure
of DTPD is shown in Fig. 1. The overall packing view of the title compound is shown in Fig S1.
The lattice and unit cell parameters are a= 13.5177(11)Å, b= 12.0829(9)Å, c= 10.7707(8)Å and
β=94.511(4)°. In this crystal structure, the intermolecular C−HꢀꢀꢀO hydrogen bonding
interactions (C8−H8AꢀꢀꢀO1 and C8−H8BꢀꢀꢀO2) occurred along ‘c’ axis is shown in Fig. 2. The

ACCEPTED MANUSCRIPT
crystal structure is further stabilized by π–π stacking interactions between aromatic rings (C1-
C6/C1-C6) with centroid-centroid and inter-planar distances of 3.830(3) and 3.564 Å
respectively and a slip angle of 1.402°. Table 1a and 1b summarizes the crystallographic data
and hydrogen bonding interactions of DTPD. The minimum and maximum value of electron
-3
residual density observed as -0.89, 1.02 e.Å and the final refinement factor of DTPD is 0.098.
4
.2 Hirshfeld surface analysis
The intermolecular interactions in crystal lattice of DTPD have been analyzed using
Hirshfeld surface and their corresponding two-dimensional fingerprint plots. Hirshfeld surface
analysis is a graphical tool used to study the hydrogen bonds, intermolecular contacts and to
estimate their importance for crystal lattice stability. Hirshfeld surface is mapped using dnorm
descriptor, when encompasses two factors namely d and d . d represent the distance between the
e
i
e
surface point to nearest interior atoms and d represent the distance between the surface point to
i
e i
nearest exterior atoms [23]. The two dimensional d /d fingerprint plots exhibit significant
differences from the interactions occurring in the crystal lattice of the DTPD molecule. To
provide context, the outline of the full fingerprint plot of DTPD is shown in grey color
background and blue dotted area shows the separate contact. The dnorm and 2D-fingerprint plot
(100% interactions) of DTPD is shown in Fig. 3. Red-blue-white color scheme mapped in
Hirshfeld surface using dnorm descriptor. Red is lesser the Van der Waals radii, blue exceeds the
Van der Waals radii and white is equal to the Van der Waals radii. The red regions in the Fig. 3,
visualize the OꢀꢀꢀH, CꢀꢀꢀH and HꢀꢀꢀC intermolecular contacts, respectively. The various fingerprint
plots of DTPD have shown in Fig. 4.
The decomposing fingerprint plot of DTPD in crystal lattice, highlighting separately the
HꢀꢀꢀH(49%), CꢀꢀꢀC(3.2%), CꢀꢀꢀO/OꢀꢀꢀC(0.4%), CꢀꢀꢀS/SꢀꢀꢀC(2.2%), OꢀꢀꢀS/SꢀꢀꢀO(0.6%), CꢀꢀꢀH/HꢀꢀꢀC
(
24.6%), HꢀꢀꢀS/SꢀꢀꢀH(5.3%) and OꢀꢀꢀH/HꢀꢀꢀO(13.4%) intermolecular contacts. The d , d , shape
e i
index and curvedness surfaces of DTPD are shown in Fig. 5. The various intermolecular contacts
are verified using d and d surfaces. The planar stacking arrangement of CꢀꢀꢀC is identified by
e
i
closer red and blue triangles from the shape index. The molecules bearing aromatic rings are
involved in πꢀꢀꢀπ contacts, which are confirmed by the presence of flat green surface areas of
CꢀꢀꢀC contribution in curvedness surface. The 3.2% contribution of CꢀꢀꢀC from the fingerprint
plot represents the π-stacking interactions in DTPD. A quite high contribution of HꢀꢀꢀH contacts
to the Hirshfeld surface is shown by aromatic moiety bearing organic molecular crystals. From

ACCEPTED MANUSCRIPT
the result, it emerges that the intermolecular interaction HꢀꢀꢀH shows major contribution 49%
from the Hirshfeld surface.
4
.3 Conformational analysis of DTPD
The various conformers of DTPD have been obtained by minimizing the potential energy
in all geometrical parameters by rotating torsion bond (C1−C11−C12−C13) angle from 0°-360°
with 10° interval using B3LYP/6-311++G(d,p) level of theory. The various conformers from the
potential energy surface scan of title molecule are shown in Fig. 6. In which two conformers at
1
80° and 360° have shown minimum potential energies about −1359.732848 and −1359.732843
hartree. Whereas, there are two conformers shown maximum potential energy (−1359.723216
and −1359.723233 hartree) at 90° and 270° torsion angle. Since at the 180° this chemical
structure has minimum energy (−1359.732848 hartree) in the potential surface, it has become a
stable structure and subjected for further investigation. The relative energies of possible
conformers of DPTD are listed in Table 2.
4
.4 NBO analysis
The donor-acceptor interactions described by the electron donation from the filled lone
pair donor NBOs of O and S atoms to empty acceptor orbitals. The more favorable interactions
of DTPD molecular system are π-π*, n-π*, π-σ* and n-σ* interactions. The highest stabilization
energy 93.26 kJ/mol is shown from donor Sulphur LP(2) S to acceptor orbital π* (C -C ).
2
0
13 14
Similarly, from the same donor S transfer energy 89.75 kJ/mol to acceptor π*(C -C ) orbital.
2
0
16 18
From NBO, the strongest interactions from the donor to acceptor NBO orbitals have found in the
second lone pair electrons of O and O . Stabilizing interactions from LP(2)O →σ*(C -C ) has
6
7
6
21
1
8
4.43 kJ/mol and LP(2)O
6
1 2
→ σ*(C -C ) has 88.49 kJ/mol stabilization energies. The stabilization
energies of 85.94 and 83.68 kJ/mol are given by the interactions from the LP(2)O →σ*(C -C )
6
4
5
and σ*(C -C ). The occupancies of the O , O and S are noted as 1.8846, 1.8868 and 1.6330.
5
32
6
7
20
The orbitals mapped overlapping of donor Oxygen and Sulphur to its corresponding acceptor
orbitals and the sum of donor-acceptor interaction orbitals are shown in Fig.7. The donor-
acceptor interactions of DTPD are summarized in Table 3.
The strong intramolecular hyperconjugative interactions occur in one phenyl ring moiety
are, π(C -C , C -C and C -C ) to π*(C -C , C -C , C -C , C -C , C -C and C -
3
0
28
26 24
22 21
2)
26 24
22 21
30 28
22 21
30 28
26
(
C ). Their corresponding E stabilization energies are 91.13, 80.83, 74.43, 90.54, 82.55 and
24

ACCEPTED MANUSCRIPT
7
9.24 kJ/mol, respectively. In addition, the interactions from bonding π(C32-C39, C33-C35 and C37-
C ) to antibonding π*(C -C , C -C , C -C , C -C , C -C and C -C ) have shown the
40
33 35
37 40
32 39
37 40
32 39
33 35
stabilization energies of 82.76, 78.16, 80.5, 90.83, 91.92 and 74.39 kJ/mol, respectively. Other
hyperconjugative interactions from the two phenyl ring to the adjacent carbonyl groups have
shown by π-π*. The donor π(C -C , C -C ) transfers electron to antibonding π*(C -O , C -O )
2
2
21
32 39
1
6
5
7
leading to stabilization energies of about 74.68 and 78.07 kJ/mol. The intramolecular interaction
in the thiophene ring system is revealed by the interactions of π(C -C )→σ*(C -C ) has 67.91
1
3
14
16 18
kJ/mol and π(C -C )→π*(C -C ) has 67.91 kJ/mol, with the occupancy ~1.87e. The weak
1
6
18
13 14
stabilization interaction energy 1.03 kJ/mol has shown by σ(C22-H23)→σ*(C22-C21). From the
NBO analysis, the DTPD molecule has Lewis structure with 97.66%, valence non-Lewis with
2
.13% and Rydberg non-Lewis with 0.20%.
4
.5 Vibrational assignments
The vibrational spectral analysis of DTPD has been performed on the basis of
characteristic vibrations of pentane-1,5-dione, phenyl and thiophene rings. The analysis of
vibrational spectra is based on the FT-IR, FT-Raman and harmonic wavenumber computed at
DFT/B3LYP/6-311++G(d,p) level of theory. The vibrational modes of DTPD have been
precisely assigned from the basis of the PED analysis using VEDA4 program. The FT-IR and
FT-Raman wavenumbers have been compared with theoretical wavenumbers and their
assignments are listed in Table 4. The experimental FT-IR and FT-Raman spectra with their
corresponding theoretical spectra are shown in Fig. 8. Proper scale factor is used to scale down
the unscaled wavenumber to bring closer to the experimental wavenumbers as suggested by
CCCBDB [24].
4
.5.1 Pentane-1,5-dione vibrations
−
1
The carbonyl stretching vibrations are expected in the spectral region of 1715-1680 cm
[25]. The carbonyl bands are the most characteristic bands of the Infrared spectra and have been
very extensively examined. There are two carbonyl groups in DTPD namely C1=O6 and
−
1
1 6
C5=O7.The medium band observed in FT-Raman spectrum at 1696 cm is assigned to νC =O
−
1
vibration of the title molecule and the theoretical wavenumber give this mode at 1690 cm with
−
1
−1
8
8% contribution of PED. Similarly, the intense band at 1683 cm /FT-IR, 1642 cm /FT-Raman
−
1
and the harmonic wavenumber at 1682 cm are the corresponding wavenumbers for the νC =O
5
7

ACCEPTED MANUSCRIPT
stretching vibration with 87% of PED. These two carbonyl vibrations have higher force constants
2
0.88 and 20.24, when compared with other vibrations. The stretching vibration of νC −H has
3 10
−
1
−1
−1
medium bands at 3000 cm in FT-IR, 3016 cm in FT-Raman and 2985 cm from the
calculated results. The C−H bonds in the methylene group combine to produce two coupled
vibrations of different frequencies, asymmetric and symmetric vibrations. The aliphatic C-H
−
1
stretching vibrations usually observed in the range of 3000-2800 cm [26]. The medium band at
−
1
−1
2
973 cm in FT-IR and as a weak band at 2940 cm in FT-Raman is assigned to asymmetric
stretching vibrations of the two methylene groups. The symmetric stretching vibrations of
−
1
−1
methylene groups are observed as a medium band at 2938 cm /FT-IR and 2930 cm /FT-
Raman, respectively. Their corresponding calculated wavenumbers are appeared in the range of
−
1
2
985-2923 cm .
The CH bending modes follow the general order of wavenumbers, CH -scissoring >
2
2
CH -wagging > CH -twisting > CH -rocking. For the –CH −C=O the scissoring vibration of
2
2
2
2
−
1
methylene group is normally occurs in the range of 1435-1405 cm [27]. The scissoring modes
−
1
of both methylene groups are calculated at 1407 cm . The various non polar concentrations have
−
1
estimated by the methylene wagging modes and are occur in 1400-1300 cm . In our present
−
1
case, the band due to methylene wagging vibration is recorded at 1325 cm in FT-IR. The
−
1
harmonic bands at 1336 and 1328 cm are assigned to the wagging modes of methylene groups.
The out-of-plane deformations such as twisting and rocking vibrations of methylene present in
−
1
ethyl group occurs at 1285-1215 and 1150-1070 cm [26]. The medium bands at 1232 and 1197
−
1
cm are assigned to twisting vibrations of the CH
2
groups. The FT-Raman peak appears at 862
−
1
cm is corresponds to rocking mode of methylene group. Their calculated wavenumbers 1225,
−
1
1
202, 944 and 858 cm have shown good agreement with the FT-IR and FT-Raman
wavenumbers.
4
.5.2 Thiophene ring vibrations
The C−S stretching vibrations of thiophene absorbs near ~675 cm , usually medium
intensity in FT-IR and strong intensity in FT-Raman spectrum. Karthick et al., reported the C–S
−
1
−
1
stretching vibrations of thiophene-2-carboxylic acid at 830 and 698 cm [28]. Li et al., assigned
−
1
C–S vibrations at 746 and 670 cm for thiophene derivative [29]. In DTPD, the C−S stretching
−
1
vibrations are observed as strong bands at 832 and 688 cm in FT-IR spectrum. Theoretically
−
1
scaled wavenumbers of 828 and 698 cm are in good agreement with experimental FT-IR. The

ACCEPTED MANUSCRIPT
−
1
medium peak identified at 706 cm in FT-IR is assigned to bending βC13−S20−C18 vibration. Its
−
1
corresponding calculated wavenumber assigned at 718 cm .
Thiophene and its derivatives give peaks in the region of 3120–3100 cm due to C−H
−
1
−
1
stretching vibration [30]. The bands calculated at 3137, 3097 and 3080 cm are assigned to C−H
stretching vibrations of the thiophene ring. Thiophene C−C stretching vibrations are observed as
−
1
−1
strong bands at 1512, 1426 cm in FT-IR and as weak band at 1503 cm in FT-Raman
spectrum. While the DFT calculations gives the thiophene C−C vibrations at 1521 and 1426
−
1
cm . PED results have shown that the C−C vibrations are strongly influenced by β
CCH
−
1
vibrations. The in-plane bending vibration of C-H observed as weak band at 1028 cm in FT-
−
1
Raman spectrum. The scaled wavenumber at 1033 cm has agreed well with the experimental
wavenumber.
4
.5.3 Phenyl ring vibrations
−
1
The aromatic ring C−C stretching vibrations are generally observed at 1600–1400 cm
−
1
[
31]. The strong bands at 1592 cm in FT-IR and the counterpart in FT-Raman spectrum
−
1
appears at 1612 cm are assigned to the νC−C stretching vibrations of the two phenyl rings. The
−
1
back to back wavenumbers at 1583 and 1565 cm are assigned for the theoretical frequencies of
the ring C−C stretching vibrations. The aromatic C–H stretching vibrations of aromatic structure
−
1
are expected to appear in the 3100–3000 cm frequency range, with multiple weak bands [32].
−
1
−1
The wavenumber calculated in the range between 3095-3090 cm and 3080-3060 cm are
corresponding to the νC−H stretching vibrations of the phenyl rings. The aromatic C−H
−
1
stretching vibrations of the DTPD are observed as medium band at 3063 cm /FT-IR and as
−
1
strong band at 3056 cm /FT-Raman spectrum, respectively. PED results reveal that these
vibrations have relatively greater than 90% of contribution.
In phenyl rings, the C−H in-plane and out-of-plane bending vibrations generally lie in the
−
1
−1
regions 1500-1100 cm and 1000-700 cm [33], respectively. The C–H in-plane bending
vibrations are observes at higher wavenumbers than the out-of-plane bending vibrations. The FT-
−
1
−1
IR bands at 1449, 1158 cm and FT-Raman band at 1445 cm are attributed to the C−H in-
plane bending vibrations of the phenyl ring. The theoretical result predicts the above said
−
1
vibrations at 1470, 1429, 1428, 1160 and 1159 cm , respectively. The C−H out-of-plane
−
1
bending vibrations are computed at 981,979, 965, 920 and 908 cm from B3LYP method. The
−
1
FT-IR band at 894 cm has coincides well with the calculated wavenumber. The trigonal

ACCEPTED MANUSCRIPT
−
1
symmetry breathing mode of the phenyl ring is observed near 1000 cm , in which only the
carbon atoms in the positions 2,4,6 are oscillating with sizeable amplitude [31]. In our present
−
1
investigation the trigonal breathing modes of two phenyl rings are calculated at 983 cm in DFT
−
1
and it shows excellent agreement with the band observed at 984 cm in FT-IR spectrum. The
−
1
ring breathing mode is observed as strong band at 1009 cm in FT-IR. The wavenumber
−
1
calculated at 1014 and 1013 cm are corresponding counterparts of the phenyl ring breathing
mode.
1
4
.6 H-NMR analysis
Density functional theory shielding calculations are rapid and applicable to large systems
1
[
34]. The H NMR chemical shifts have been calculated using Gauge independent atomic
orbitals. The theoretical NMR chemical shifts repositioned using proper scale factors [35]. The
1
recorded H-NMR spectrum of DTPD is shown in Fig. S2. The theoretical and experimental
1
chemical shifts of DTPD are listed in Table 5. In H-NMR spectrum, the signal belonging to
aliphatic C H proton has observed between 4.388-4.479 ppm as pentet. For the same proton,
1
6
17
the chemical shift calculated at 4.294 ppm and shows good agreement with the experimental
1
chemical shift. The most characteristic signal in H-NMR spectrum observed between 3.386-
3
.575 is belongs to two methylene group present in the pentandione moiety. The two doublet of
doublet observed in this range is due to the vicinal and germinal couplings of the non-equivalent
protons of methylene groups with aliphatic proton H . The theoretical chemical shifts at 3.144-
1
0
3
.599 ppm are the corresponding methylene protons signal of DTPD. The multiplets observed at
the range of 6.863-7.132 ppm are of thiophene ring protons peaks. The ten protons of two phenyl
rings shows multiplet at the spectral range of 7.428-7.989 ppm. The aromatic protons of DTPD
are computed in the range of 6.716-8.336 ppm. Totally, eighteen protons have identified from the
1
recorded H-NMR spectrum of DTPD.
4
.7 Energy gap analysis
The good approximation about the reactivity of the molecule could be found by looking
the frontier molecular orbitals (FMO). The highest occupied molecular orbitals (HOMO) and the
lowest unoccupied molecular orbitals (LUMO) are labelled as frontier molecular orbitals.
HOMO is plausibly viewed as electron donating or nucleophilic, while the LUMO is electron
accepting or electrophilic in nature. The energy gap between the HOMO and LUMO determines

ACCEPTED MANUSCRIPT
the chemical stability of a molecule and charge transfer occurs within the molecule [36].
HOMO-LUMO energy gap is generally the lowest energy electronic excitation that is possible in
a molecule. It is known from Fig. 9, the HOMO is mainly localized on the thiophene ring and
pentan-1,5-dione of the DTPD molecular system. Whereas the LUMO is mainly localized on the
phenyl ring and −COCH − group of the title molecule. These frontier molecular orbitals indicate
2
2
the electron density transfer from thiophene to phenyl ring through the −CHCOCH − linkage.
The red regions represent the positive phases and the green regions represent negative phases of
DTPD. The energies of HOMO and LUMO are calculated as -5.9650 and -1.6000 eV,
respectively. The energy gap of DTPD is calculated as 4.3650 eV. The energies of HOMO-1 and
LUMO+1 is calculated as -6.5509 and -1.3552 eV, its energy gap is 5.1975 eV. The frontier
molecular orbitals and their energies of DTPD are listed in Table S1.
Energies of the FMOs used for the determination of global reactivity descriptors [37-40].
Parr et al., [41] have proposed electrophilicity index as a quantity of energy lowering due to
maximal electron flow between donor and acceptor. According to Koopman’s theorem,
Ionization energy I = −EHOMO and electron affinity A = −ELUMO. By using the values of I and A,
we can calculate the global reactivity descriptors such as, chemical hardness (η = I−A/2),
2
electronegativity (χ = I+A/2), chemical potential (ꢁ = −(I+A)/2), electrophilicity index (ω =ꢁ /2η)
and softness (s = 1/η). The global reactivity descriptors of DTPD are calculated as, Ionization
potential I = 5.9650 eV, electron affinity A = 1.6000 eV, η = 2.1825 eV, χ = 3.7825 eV, ꢀ = -
3
.7825 eV, ω = 3.2777 eV and s = 0.4581 eV, respectively. Based on the narrow energy gap and
its chemical hardness (η) value 2.1825 eV of DTPD, we conclude that this molecule can be
classified as hard molecule. Electrophilicity index ω→3.2777 eV shows the global electrophilic
nature of the DTPD.
4
.8 Nonlinear optical study
Organic molecules showing higher hyperpolarizabilities exhibit larger NLO potential and
used in variety of optical devices. Theoretical identification of first hyperpolarizability is useful
in understanding the correlation between the molecular geometry and NLO properties. This
method helps to design novel organic NLO materials effectively. The total static dipole moment
ꢁ
, the anisotropy of the polarizability ∆α and the mean first hyperpolarizability β , using the x-,
0
y- and z-components are defined as:

ACCEPTED MANUSCRIPT
ꢃ
ꢃꢁꢁꢁ
ꢃ
µ=ꢀ(ꢁμ + μ + μ )
(2)
ꢂ
ꢄ
ꢅ
ꢃ
ꢈ/ꢃ
∆
ꢆ = 2ꢇꢈ/ꢃ[(ꢆ − ꢆ )2 + (ꢆ − ꢆ )2 + (ꢆ − ꢆ )2+6 ꢃ
α
+ 6αꢃ + 6α ]
(3)
(4)
ꢉꢉ
ꢊꢊ
ꢊꢊ
ꢋꢋ
ꢋꢋ
ꢉꢉ
ꢌꢍ
ꢈ
ꢌꢎ
ꢎꢍ
ꢃ
ꢃ
ꢃ
ꢐ
ꢃ
ꢁ
ꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁꢁβ = (β + β + β )ꢁ
ꢏ
ꢂ
ꢄ
ꢅ
Where,
βꢏ = [(βꢂꢂꢂ + βꢂꢄꢄ + βꢂꢅꢅ)ꢁꢃ + (βꢎꢎꢎ + βꢄꢅꢅ + βꢄꢂꢂ)ꢁꢃ + (βꢍꢍꢍ + βꢅꢂꢂ + βꢅꢄꢄ)ꢁ ] ꢁꢁ(5)
ꢃ ꢈ/ꢃ
Organic materials are frequently formed by weak Van der Waals interactions and
hydrogen bonds. Hence it possesses a higher degree of delocalization. For DTPD, the dipole
z y
moment value is higher in ꢁ and lower in ꢁx, ꢁ components indicating the charge imbalance
along Z-axis. The total dipole moment of title molecule is calculated as 4.8179 Debye. The first
hyperpolarizability components of title molecule are listed in Table 6. The molecular
-30
polarizability and first hyperpolarizability of DTPD are calculated as 0.65 and 12.84 x10 esu (1
-33
a.u = 8.6393×10 esu), respectively. The first hyperpolarizability value of DTPD is thirty four
-30
times greater than the reference NLO molecule urea (0.3718 x10 esu). The DFT calculation
results show that the DTPD might have a good nonlinear optical response and its structure with
molecular axis is shown in Fig. 10.
4
.9 Molecular electrostatic potential
The molecular electrostatic potential is related to the electron density and it is a useful
descriptor in determining the electrophilic/nucleophilic charge sites and hydrogen bonding
interactions [45]. The molecular electrostatic potential mapped surface of DTPD is shown in
Fig. 11. The red regions (negative) in MEP shows the electrophilic reactivity and the blue
regions (positive) represent the nucleophilic reactivity of the title molecule. The green regions
are neutrally charged surface of DTPD. The negative regions are mainly localized over the
oxygen atoms of the pentadione. The negative regions are not intensively observed for the title
molecule and relatively observed near methylene hydrogens. The MEP map of DTPD shows that
the negative potential sites are on electronegative atoms. Similarly, the positive potential sites are
around the carbon and hydrogen atoms. The noncovalent interactions are identified using these
charged regions of DTPD.

ACCEPTED MANUSCRIPT
5
. Conclusion
In this work, we synthesized a novel bischalcone derivative effectively for nonlinear
optical properties. Pure DTPD single crystals have been successfully grown by slow evaporation
method using ethanol as solvent. The solid state structure adopts monoclinic system with P2 /c
1
space group. The Hirshfeld surfaces and fingerprint plots pointed out that the structure of DTPD
is stabilized by various contacts such as HꢀꢀꢀH, CꢀꢀꢀC, CꢀꢀꢀO/OꢀꢀꢀC, CꢀꢀꢀS/SꢀꢀꢀC, OꢀꢀꢀS/SꢀꢀꢀO,
CꢀꢀꢀH/HꢀꢀꢀC, HꢀꢀꢀS/SꢀꢀꢀH and OꢀꢀꢀH/HꢀꢀꢀO interactions. The 3.2% of linear stacking arrangement of
DTPD has visualized from shape index and curvedness surfaces. The stable molecular
conformation, FT-IR, FT-Raman, NMR and various properties have been worked out using
DFT/B3LYP/6-311++G(d,p) level of theory. The optimized stable structure of DTPD has
identified at 180° with energy of −1359.73284852 hartree. The stabilization aroused from donor-
acceptors of DTPD analyzed from NBO analysis. The vibrational profile of DTPD has been
identified with the help of PED analysis. The semiconducting property of the title molecule is
explored by the energy gap of 0.4365 eV (0 < E < 5 eV). The nonlinear optical property of
g
-30
DTPD is calculated as 12.84 x10 esu, which is thirty four times greater than reference
molecule urea. Hence DTPD has excellent nonlinear optical property. Molecular charge sites of
title molecule have identified using molecular electrostatic potential.
Supplementary materials
CCDC 1549923 contains the supplementary crystallography data for this title molecule. These
data can be obtained free of charge from the Cambridge Crystallography Data Centre via
www.ccdc.cam.ac.uk/data request/cif.

ACCEPTED MANUSCRIPT
6
. References
S. Shetharam, G. Umesh, K. Chandrasekharan, B. K. Sarojini, Opt. Mater., 30 (2008)
297-1303.
S. Shettigar, K. Chandrasekharan, G. Umesh, B. K. Sarojini, Polymer, 47 (2006) 3565-
567.
A. Delavaux, B. Nicot, J. Maynadie, D. Lavabre, J. Organometalic. Chem., 692 (2007)
74-886.
1
2
3
.
1
.
.
3
8
4
5
6
.
.
.
E. I. Gasull, S. E. Blanco, F. H. Ferretti, J. Mol. Struct. (Theochem), 579 (2002) 121-137.
B. Zhao, W. O. Lu, Z. H. Zhou, Y. Wu, J. Mater. Chem., 10 (2000) 1513-1517.
S. D. Bella, I. Fragala, I. Ledoux, M. A. D. Garcia, T. J. Marks, J. Am. Chem. Soc., 119
(1997) 9550-9557.
7
8
9
1
1
.
P.S. Patil, S.M. Dharmaprakash, K. Ramakrishna, H. K. Fun, R. Sai SanthoshKumar, D.
Narayana Rao, J. Cryst. Growth, 303 (2007) 520-524.
.
V. Crasta, V. Ravindrachary, R. F. Bhajantri, R. Gonsalves, J. Cryst. Growth, 267 (2004)
1
29-133.
P. S. Patil, S. M. Dharmaprakash, H. K. Fun, M. S. Karthikeyan, J. Cryst. Growth,
97(2006) 111-116.
.
2
0.
1.
A. M. Asiri, H. M. Marwani, K. A. Alamary, M. S. Ala Amondi, S. A Khan and S. A. El-
dely, Int. J. Electrochem. Sci, 9 (2014) 799-809.
J. Badan, R. Hierle, A. Perigaud, J. Zyss, “Nonlinear Organic Crystals: Theoretical
Concepts, Materials, and Optical Properties”, in: D. J. Williams (Ed.), Nonlinear

ACCEPTED MANUSCRIPT
Optical Properties of Organic Molecules and Polymeric Materials, 233 D. 5, American
Chemical Society, Washington, DC, (1983) 81-107.
1
1
1
1
1
1
2.
3.
4.
5.
6.
7.
D.S. Chemla, J. Zyss, Nonlinear Optical Properties of Organic Molecules and Crystals,
vols. 1-2, Academic Press, New York, 1987.
S. Shettigar, S. Chandrasekaran, G. Umesh, B. K. Sarojini and B. Narayana, Polymer 47
(2006) 3565-3567.
R. Chauhan, R. Yadav, A. K. Singh, M. Trivedi, G. K. Kohn, A. Kumar, S. Gosavi and S.
Rane, RSC Adv., 6 (2016) 97664-97675.
R. Zhang, M. Wang, H. Sun, R. Usman, S. Wang, X. Gu, J. Wang and C. Xu, New J.
Chem. 40 (2016) 6441-6450.
M. Shkir, S. Muhammad, S. AlFaify, A. Irfan, P. S. Patil, M. Arora, H. Algarni, and Z.
Jingping, RSC Adv., 5 (2015) 87320-87332.
Gaussian 09, Revision A.1, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H.
Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L.
Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta,
F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R.
Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J.
Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, 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, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G.
A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B.
Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT,
2
009.
1
8.
M. H. Jamroz, Vibrational Energy Distribution Analysis: VEDA4 program, Warsaw,
Poland, 2004.
1
2
2
9.
0.
1.
D. Michalska, Raint Program, Wroclaw University of Technology, 2003.
D. Michalska and R. Wysokinski, Chem. Phys. Lett., 403 (2005) 211-217.
S. K. Wolff, D. J. Grimwood, J. J. McKinnon, M. J. Turner, D. Jayatilaka and M. A.
Spackman, CrystalExplorer3.1, University of Western Australia, 2012.
E. D. Glendening, A. E. Reed, J. E. Carpenter, and F. Weinhold. NBO Version 3.1.
2
2
2.
3.
J. Dalal, N. Sinha, H. Yadav, B. Kumar, RSC Adv, 5 (2015) 57735-57748.

ACCEPTED MANUSCRIPT
2
4.
Russell D. Johnson III (Ed.), NIST Computational Chemistry Comparison and
Benchmark Database, NIST Standard Reference Database Number 101, Release 17b,
September 2015.
2
2
5.
6.
N.P.G. Roeges, A Guide to Complete Interpretation of IR Spectra of Organic Structures,
Wiles, New York, 1994.
G. Socrates, Infrared and Raman Characteristic Group Frequencies, 3rd Ed., John Wiley
&
Sons, Inc., USA, 2004.
2
2
2
3
3
7.
8.
9.
0.
1.
R. Zbinden, Infrared Spectra of Polymers, Academic Press, New York, 1964.
T. Karthick, V. Balachandran, and S. Perumal, SpectrochimActa A, 141 (2015) 104-112.
X. H. Li and X. Z. Zhang, SpectrochimActa A, 105 (2013) 280-287.
A. S. Braterman, Metal Carbonyl Spectra, Academic Press. New York, 1975.
G. Varsanyi, Vibrations Spectra of Benzene Derivatives, Academic Press, New York,
USA, 1969.
3
3
2.
3.
M. Jag, Organic Spectroscopy - Principles and Applications, second ed., Narosa
Publishing House, New Delhi, 2001.
A. Dhandapani, S. Manivarman, S. Subashchandrabose, Chem Phys Lett, 655-656 (2016)
1
7–29.
3
3
4.
5.
I. A. Konstantinov and L. J. Broadbelt, J. Phys. Chem. C, 115 (2011) 12364-12372.
H. Singh, S. Singh, A. Srivastava, P. Tandon, Spectrochim. Acta A,120 (2014) 405-415.
3
3
3
3
4
4
4
6.
7.
8.
9.
0.
1.
2.
F.V. Lewis, C. Ioannides, D.V. Parka, Xenobiotica 24 (1994) 401-408.
T. Koopmans, Physica 1 (1934) 104-113.
R.S. Mulliken, J. Chem. Phys. 2 (1934) 782-793.
R. G. Pearson, J. Am. Chem. Soc. 107 (1985) 6801-6906.
W. Yang, R. G. Parr, Proc. Nat Acad Sci, 82 (1985) 6723-6726.
R. Parr, L.V. Szentpaly, S. Liu, Am. Chem. Soc. 121 (1999) 1922-1924.
F. Guegan, P. Mignon, V. Tognetti, L. Joubert, and C. Morell, Phy Chem Chem Phys, 16,
(2014) 15558-15569.

ACCEPTED MANUSCRIPT
Table 1a Crystallographic data and structure refinement parameters of DTPD.
Crystal Data of DTPD
Molecular formula
C H O S
21 18 2
M
r
334.42
Crystal system
Space group
a, b, c (Å)
Monoclinic
P21/c
13.5177(11), 12.0829(9), 10.7707(8)
α, β, γ (˚)
V(Å )
90, 94.511(4), 90
1753.8 (2)
3
Z
4
Radiation Type
Mo Kα
0.19
‒
1
ꢀ
(mm )
Crystal size (mm)
Diffractometer
0.50 × 0.45 × 0.40
Bruker kappa Apex II CCD Diffractometer
Absorption correction
Multi-scan' SADABS (Bruker, 1999)
Data Collection
296
Temperatue (K)
T , T
Reflections [I > 2σ(I)]
Dataset
Rint
0.909, 0.927
25324, 4325, 2517
-18: 18 ; -16: 16 ; -13: 12
0.030
min
max
−
1
(Sin θ/λ)max (Å )
0.615
Refinement
2
2
2
Refinement R[F >2σ(F )], wR(F ), S 0.098, 0.363, 1.05
No. of reflections
No. of parameters
No. of restraints
H-atom treatment
4325
217
0
H atom parameters constrained
1.02, -0.89
-3
∆ρmax, ∆ρmin (e Å )
Table. 1b Hydrogen bonding geometry of the DTPD.
D−H···A
D−H
H···A
D···A
D−H···A
i
C8−H8AꢀꢀꢀO1
C8−H8BꢀꢀꢀO2
0.9700
0.9700
2.4600
2.4800
3.353(5)
3.088(5)
153.00
121.00
Symmetry Codes: (i) x,3/2-y,-1/2+z

ACCEPTED MANUSCRIPT
Table 2 The various possible conformers and its relative energies of DTPD.
Rotation ( °)
Relative energy
Hartree)
(
0
-1359.732843
-1359.732773
-1359.732274
-1359.731317
-1359.729942
-1359.728307
-1359.726536
-1359.724836
-1359.723590
-1359.723217
-1359.723872
-1359.725290
-1359.726962
-1359.728568
-1359.729940
-1359.731004
-1359.731915
-1359.732544
-1359.732849
-1359.732753
-1359.732217
-1359.731208
-1359.729811
-1359.728143
-1359.726370
-1359.724699
-1359.723529
-1359.723234
-1359.723998
-1359.725505
-1359.727242
-1359.728838
-1359.730099
-1359.731073
-1359.731934
-1359.732536
-1359.732843
1
2
3
4
5
6
7
8
9
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
00
10
20
30
40
50
60
70
80
90
00
10
20
30
40
50
60
70
80
90
00
10
20
30
40
50
60

ACCEPTED MANUSCRIPT
Table 3 The donor-acceptor interactions of DTPD.
Acceptor
F(j-i) F(i,j)
Type
Donor (i)
ED/e
ED/e kJ/mol kCal/mol
(j)
a.u
a.u
σ -σ*
C30-H31
1.9803 C30-C21
C28-C26
C22-C21
1.6508 C26-C24
C22-C21
1.9827 C30-C21
C26-C24
1.9830 C30-C28
C24-C22
1.6517 C30-C28
C22-C21
1.6430 C30-C28
C26-C24
0.0214
0.0163
0.0228
0.3228
0.3687
0.0214
0.0158
0.0146
0.0154
0.2873
0.3687
0.2873
0.3228
0.1261
0.0228
0.3687
0.0090
0.0209
0.0163
0.0123
0.3064
0.1323
0.2865
0.3206
0.3712
0.3206
0.0216
0.0158
0.3712
0.2865
0.0659
0.0608
0.0606
0.0654
0.0606
0.0654
0.0222
0.0152
0.3064
0.2943
4.48
15.44
18.16
91.13
80.83
15.86
14.9
14.73
15.19
74.43
90.54
82.55
79.24
74.68
4.94
1.07
3.69
4.34
21.78
19.32
3.79
3.56
3.52
3.63
17.79
21.64
19.73
18.94
17.85
1.18
4.86
1.29
1.31
4.1
1.09
1.09 0.057
1.09 0.061
0.03
π -π*
σ -σ*
σ -σ*
π -π*
π -π*
C30-C28
C28-H29
C26-H27
C26-C24
C22-C21
0.28
0.07
0.28 0.066
1.1 0.058
1.1 0.056
1.12 0.056
1.11 0.057
0.29 0.065
0.28
0.07
0.29 0.068
0.28 0.066
0.28 0.067
C1-O6
σ -σ*
π -π*
σ -σ*
σ -σ*
C1-O6
C1-O6
C2-H9
C13-S20
1.9955 C22-C21
1.9735 C22-C21
1.9601 C1-O6
1.9764 C2-C3
C14-H15
1.65
0.04
20.33
5.4
5.48
0.4 0.043
1.1 0.034
1.02 0.033
1.13 0.061
1.15 0.049
0.3 0.062
0.27 0.067
0.29 0.069
0.28 0.065
0.28 0.066
17.15
11.13
60.21
78.07
82.76
78.16
80.5
90.83
15.94
14.9
91.92
74.39
84.43
88.49
6.86
C18-H19
2.66
π -π*
π -π*
C16-C18
C32-C39
1.8858 C13-C14
1.6424 C5-O7
C33-C35
C37-C40
1.6505 C32-C39
C37-C40
1.9826 C32-C33
C37-C40
1.6481 C32-C39
C33-C35
1.8846 C21-C1
C1-C2
1.9769 C4-C5
C5-C32
1.8868 C4-C5
C5-C32
1.9840 C13-C14
C16-C18
1.6330 C13-C14
C16-C18
14.39
18.66
19.78
18.68
19.24
21.71
3.81
π -π*
σ -σ*
π -π*
n -σ*
n -σ*
n -σ*
n -σ*
n -π*
C33-C35
C35-H36
C37-C40
LP(2) O6
LP(1) O7
LP(2) O7
LP(1) S20
LP(2) S20
0.28
0.07
1.09 0.058
1.1 0.056
0.28 0.071
0.29 0.065
0.69 0.107
0.65 0.106
1.07 0.038
3.56
21.97
17.78
20.18
21.15
1.64
1.72
20.54
20
2.11
1.92
22.29
21.45
7.2
1.12
0.04
85.94
83.68
8.83
8.03
93.26
89.75
0.65 0.105
0.7 0.107
1.24 0.046
1.24 0.044
0.27
0.27 0.069
0.07

ACCEPTED MANUSCRIPT
Table 4 The fundamental vibrational assignments of DTPD.
Vibrational wavenumber
FT-
Sl.
No
Reduced
Mass
Force
Constant
PED≥10%
unscaled scaled FT-IR
Raman
1
3244
3203
3200
3200
3196
3195
3185
3185
3185
3175
3174
3165
3164
3087
3069
3053
3034
3023
1748
1739
1637
1637
1618
1618
3137
1.10
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.10
1.10
1.06
1.06
11.60
11.36
5.49
5.49
5.47
5.45
6.81
6.61
6.60
6.60
6.58
6.58
6.53
6.53
6.51
6.47
6.47
6.41
6.40
6.10
6.09
6.03
5.75
5.71
20.88
20.24
8.68
8.67
8.44
8.41
νC H (95)
18 19
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
3097
νC H (98)+νC H (93)
14 15 16 17
3095
νC H (82)+νC H (96)
30 31 28 29
3094
νC H (79)+νC H (98)
33 34 35 36
3090
νC H (90)+νC H (83)
24 25 22 23
3090
νC H (91)+νC H (93)
40 42 39 41
3080
νC H (93)+νC H (98)+νC H (89)
39 41 35 36 37 38
3080
νC H (96)+νC H (84)+νC H (83)+νC H (98)
28 29 26 27 22 23 14 15
3080
νC H (98)+νC H (93)
14 15 16 17
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
3070
νC H (91)+νC H (93)+νC H (98)
40 42 39 41 35 36
3070
νC H (96)+νC H (90)
28 29 24 25
3061 3063m
3060
νC H (91)+νC H (98)+νC H (89)
40 42 35 36 37 38
3056s
νC H (96)+νC H (84)+νC H (90)
28 29 26 27 24 25
2985 3000m 3016m
νC H (85)
3 10
2967
2973m
νC H (90)+νC H (96)
2 8 2 9
2953 2940w
νC H (95)+ νC H (98)
4 11 4 12
2934 2938m 2930vs
2923
νC H (90)+ νC H (96)
2 8 2 9
νC H (95)+ νC H (98)
4
11
4
12
1690
1696m
νO C (88)
6 1
1682 1683vs 1642vs
νO C (87)
7 5
1583 1592vs 1612vs
νC C (34)+νC C (32)
30 28 24 22
1583
1565
1565
νC C (43)+νC C (53)
33 35 40 39
νC C (45)+νC C (48)+ νC C (23)+νC C (28)+βH C C (66)
28
26
26 24
22 21
30 21
27 26 28
νC C (43)+νC C (42)+νC C (25)+νC C (19)+βH C C (66)
35
37
37 40
32 39
32 33
38 37 40

ACCEPTED MANUSCRIPT
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
1573
1520
1520
1478
1477
1475
1455
1455
1404
1382
1373
1354
1350
1348
1335
1333
1312
1267
1243
1226
1214
1200
1199
1185
1183
1181
1133
1107
1521 1512s 1503w
5.00
2.15
2.16
2.21
2.20
6.07
1.09
1.10
1.59
1.67
2.07
1.61
2.06
2.52
2.53
2.24
1.40
1.38
1.95
2.12
1.70
1.20
1.16
1.20
1.12
1.24
2.03
1.65
7.29
2.93
2.94
2.85
2.83
7.78
1.36
1.37
1.85
1.88
2.30
1.74
2.21
2.70
2.66
2.34
1.41
1.31
1.78
1.88
1.48
1.02
0.99
1.00
0.93
1.02
1.53
1.19
νC C (68)+νC C (64)+βH C C (53)
16 18 13 14 15 14 13
1470
βH C C (34)+βH C C (45)+βH C C (35)+βH C C (45)
34 33 32 42 40 39 41 39 40 36 35 33
1470
βH C C (38)+βH C C (37)+βH C C (44)+βH C C (43)
31 30 28 29 28 30 25 24 22 23 22 24
1429 1449s 1445w
1428
νC C (43)+νC C (53)+βH C C (45)+βH C C (45)+βH C C (66)
33 35 40 39 42 40 39 36 35 33 38 37 40
νC C (34)+νC C (32)+βH C C (37)+βH C C (66)+βH C C (44)
30
28
24 22
29 28 30
27 26 28
25 24 22
1426 1426s
1407
νC C (68)+νC C (64)+νC C (50)+βH C C (48)
16 18 13 14 14 16 17 16 18
βH C H (80)+βH C H (84)
8
2
9
11
4
12
1407
βH C H (80)+βH C H (84)
8 2 9 11 4 12
1357 1366s
1336
βH C C (51)
10 3 13
βH C C (20) βH C C (68)+ τC C C H (61)
8
2
1
8
2
9
3
2
13 10
1328 1325m
1310 1312w
1306
νC14C16(50) +ΓH C C C (27)+βH C C (13)
9 2 3 4 11 4 5
βH C C (34)+βH C C (51)
34
33 32
10
3
13
βH C C (38)+βH C C (43)
31
30 28
23 22 24
1303
ΓH C C C (16)
12 4 3 2
1291
νC C (25)
32 39
1289 1277s
1268 1251s 1267m
νC C (23)+ νC C (28)
22 21 30 21
τC C C H (61)+ΓH C C C (16)
3
2
13 10
12
4
3
2
1225
1232m
1197m
βH C C (53)+βH C C (48)+βH C C (68)
15 14 13 17 16 18 11 4 12
1202
νC C (48)+βH C C (45)+ τC C C H (61)
21 1 8 2 9 3 2 13 10
1186 1187m
1174
νC C (48)+ΓH C C C (27)
21 1 9 2 3 4
1178m
νC C (13)
5 32
1160
βH C C (34)+βH C C (45)+βH C C (35)
34 33 32 42 40 39 41 39 40
1159 1158w
1146
βH C C (38)+βH C C (44)+βH C C (43)
31 30 28 25 24 22 23 22 24
βH C C (37)+βH C C (66)
29
28 30
27 26 28
1144
βH C C (45)+βH C C (66)
36 35 33 38 37 40
1142 1126vs 1118m
βH C C (66)
27 26 28
1095
1071
νC C (15)
3 13
νC C (53)
40
39

ACCEPTED MANUSCRIPT
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
1106
1100
1086
1068
1049
1048
1036
1017
1017
1015
1012
998
1070
1.57
1.39
2.38
2.00
2.08
2.03
2.81
6.10
6.03
1.34
1.35
1.39
3.01
1.41
3.90
2.44
1.49
1.48
1.34
2.53
1.26
1.26
3.93
1.77
2.37
4.56
1.96
1.68
1.14
νC C (43)+νC C (53)
33 35 40 39
1064
0.99
1.66
1.34
1.35
1.32
1.78
3.71
3.67
0.82
0.81
0.82
1.76
0.82
2.24
1.37
0.80
0.77
0.65
1.17
0.55
0.55
1.70
0.73
0.94
1.73
0.69
0.58
νC C (26)+βH C C (48)+βH C C (68)
2 3 17 16 18 19 18 16
1050
νC C (40)+βH C C (68)
3 4 19 18 16
1033
1028w
νC C (50)+νC C (40)+ βH C C (53)
14 16 3 4 15 14 13
1014
νC C (43)+ νC C (42)
35 37 37 40
1013 1009s
1001
νC C (45)+νC C (48)
28 26 26 24
βC C C (40)
13
14 16
983 984vw
983
βC C C (66)+βC C C (41)+βC C C (40)+βC C C (45)
28 26 24 35 37 40 32 39 40 30 21 22
βC C C (66)+βC C C (41)+βC C C (40)+βC C C (45)
28
26 24
35 37 40
32 39 40
30 21 22
981
ΓH C C H (87)+ΓH C C H (64)
38 37 40 42 34 33 35 36
979
τC C C H (87)+ΓH C C H (71)+ τC C C H (69)+ΓH C C H (82)
30 28 21 31 29 28 26 27 26 28 24 27 27 26 24 25
965
τC C C H (82)+ΓH C C H (87)+ τC C C H (76)
33 32 35 34 38 37 40 42 39 32 40 41
997
964
νC C (41)
1 2
994
962
τC C C H (87)+ΓH C C H (82)+ τC C C H (73)
30 28 21 31 27 26 24 25 22 24 21 23
989
956
νC C (28)
4 5
977
944
βH C H (80)+γO C C C (21)
8 2 9 6 21 2 1
951
920
τC C C H (82)+ τC C C H (76)+ τC C C H (60)
33 32 35 34 39 32 40 41 37 35 40 32
939
908 894w
876
τC C C H (87)+ τC C C H (69)+ τC C C H (73)
30 28 21 31 26 28 24 27 22 24 21 23
906
ΓH C C H (73)
15 14 16 17
887
858
862m
841m
νC C (26)+ βH C H (80)+γO C C C (52)
2 3 11 4 12 7 4 32 5
862
834
τC C C H (82)+ΓH C C H (87)+ τC C C H (76)
33 32 35 34 38 37 40 42 39 32 40 41
859
831
τC C C H (87)+ΓH C C H (71)+ΓH C C H (82)+ τC C C H (73)
30 28 21 31 29 28 26 27 27 26 24 25 22 24 21 23
856
828 832s
806
νS C (89)+βC C C (31)
20 18 14 16 18
834
ΓH C C C (79)
15 14 16 18
821
794 788w
776
788m
νC C (28)+ΓH C C C (79)
4 5 15 14 16 18
803
νC C (48)+νC C (41)+βC C O (47)+βC C C (66)
21 1 1 2 2 1 6 28 26 24
771
745 756m
742 737m
τC C C H (69)+ΓC C C C (69)
26 28 24 27 28 30 21 22
767
τC C C H (82)+ τC C C H (60)+ΓC C C C (70)
33 32 35 34 37 35 40 38 32 39 40 37

ACCEPTED MANUSCRIPT
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
9
9
9
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
743
722
703
702
695
678
663
632
632
609
595
585
552
536
495
478
436
424
421
410
410
398
314
302
250
232
215
168
718 706m
698 688s
680
7.05
3.80
1.89
1.89
1.19
5.91
6.68
6.41
6.39
3.62
3.90
2.90
3.08
4.00
3.41
5.94
5.74
3.18
3.23
2.86
2.88
5.36
5.76
6.00
4.92
2.81
3.54
5.85
2.29
1.17
0.55
0.55
0.34
1.60
1.73
1.51
1.50
0.79
0.82
0.59
0.55
0.68
0.49
0.80
0.64
0.34
0.34
0.28
0.29
0.50
0.34
0.32
0.18
0.09
0.10
0.10
βC S C (69)+βC C C (30)+βC C C (40)
13 20 18 14 16 18 13 14 16
νS C (45)
20
13
ΓC C C C (83)+ΓC C C C (70)
32
33 35 37
32 39 40 37
679
ΓC C C C (69)+ΓC C C C (64)
28 30 21 22 28 26 24 22
672
ΓH C C C (79)+ΓH C C C (73)
15 14 16 18 19 18 16 14
655
βC C O (47)+βC C C (66)+βC C C (45)
2 1 6 28 26 24 30 21 22
641 649m
611
636w
609w
νS C (45)+βC C O (46)
20 13 32 5 7
βC C C (85)+βC C C (50)+βC C C (40)
26
24 22
37 40 39
32 39 40
611
βC C C (85)+βC C C (50)
26 24 22 37 40 39
589 597m
576
ΓC C C C (55)
13 14 16 18
ΓC C C C (55)
13
14 16 18
566 564w
533 530w
519
ΓC C C C (64)+ΓC C C C (76)+ τO C C C (52)
35 37 40 39 5 32 39 40 6 4 32 5
βC C C (40)+ΓH C C O (18)
13
14 16
8
2
1
6
503w
βC C C (47)+ΓC C C S (76)
13 3 4 14 16 18 20
479
βC C C (44)
21 1 2
462 442vw
422
βC C O (46)+ΓC C C S (76)
32 5 7 14 16 18 20
ΓC C C C (64)
35
37 40 39
410
ΓC C C C (64)+ΓC C C C (64)+ τO C C C (52)
28 26 24 22 35 37 40 39 7 4 32 5
407
ΓC C C C (64)+ΓC C C C (64)
28 26 24 22 35 37 40 39
1
1
1
1
1
1
1
1
1
00
01
02
03
04
05
06
07
08
397
402vw
303w
ΓC C C C (69)+ΓC C C C (64)
28 30 21 22 26 24 22 21
396
ΓC C C C (83)+ΓC C C C (70)+ΓC C C C (64)
32 33 35 37 32 39 40 37 26 24 22 21
384
νC C (48)+βC C C (45)+ΓC C C S (76)
21 1 30 21 22 14 16 18 20
304
βC C O (47)+βC C C (47)
2 1 6 30 21 1
292
βC C O (46)+βC C C (50)+βC C C (49)
32 5 6 5 32 39 3 4 5
241
βC C C (47)+ΓC C C C (61)
13 3 4 3 13 14 16
224
βC C C (49)+βC C C (47)+ΓC C C C (18)
3 13 14 30 21 1 2 3 4 5
208
βC C C (49)+βC C C (26)
3 13 14 2 3 4
163
βC C C (49)+ΓC C C C (61)+ΓC C C C (66)
3 4 5 3 13 14 16 28 30 21 1

ACCEPTED MANUSCRIPT
109
110
111
112
113
114
115
116
117
118
119
120
157
148
142
114
68
152
143
138
111
66
4.71
5.71
5.50
4.10
7.22
7.75
5.19
3.88
4.42
4.99
7.79
6.15
0.07
ΓC C C C (76)
5 32 39 40
0.07
0.07
0.03
0.02
0.02
0.01
0.00
0.00
0.00
0.00
0.00
ΓC C C C (66)
28 30 21 1
βC C C (50)+βC C C (35)+ΓC C C C (76)
5
32 39
4
5
32
5
32 39 40
103vs
βC C C (47)+βC C C (44)+βC C C (19)
30 21 1 21 1 2 1 2 3
ΓC C C C (83)+ΓC C C C (55)
4
5
32 39
13
3
4
5
61
59
ΓC C C C (61)+ΓC C C C (86)+ΓC C C C (57)
3 13 14 16 30 21 1 2 1 2 3 4
50
48
βC C C (35)+βC C C (47)+βC C C (49)+ΓC C C C (61)
4 5 32 13 3 4 3 4 5 3 13 14 16
35
33
ΓC C C C (83)+ΓC C C C (55)
4 5 32 39 13 3 4 5
28
27
ΓC C C C (85)+ΓC C C C (86)+ΓC C C C (57)
14 13 3 4 30 21 1 2 21 1 2 3
22
21
ΓC C C C (85)+ΓC C C C (61)+ΓC C C C (86)+ΓC C C C (57)
14 13 3 4 3 4 5 32 30 21 1 2 1 2 3 4
20
19
ΓC C C C (85)+ΓC C C C (61)+ΓC C C C (57)
14 13 3 4 3 4 5 14 21 1 2 3
16
15
βC C C (26)+ΓC C C C (61)+ΓC C C C (57)
2 3 4 3 4 5 32 21 1 2 3

ACCEPTED MANUSCRIPT
Table 5 The calculated and experimental Chemical shifts of DTPD.
1
H-NMR
Atoms
Calc.
3.144
3.226
3.416
3.599
4.294
6.716
6.762
6.850
7.310
7.328
7.377
7.393
7.433
7.444
7.761
7.782
8.227
8.336
Exp.
1
1
2H
1H
3
.386-3.465
8
H
3
.497-3.575
9
H
10H
15H
17H
19H
25H
42H
29H
27H
38H
36H
23H
41H
31H
34H
4.388-4.479
6.863-7.132
7
.428-7.989

ACCEPTED MANUSCRIPT
Table 6 The first hyperpolarizability components of DTPD.
β
components
βxxx
Value
(a.u)
282.6671
610.5776
-135.1911
438.7840
-143.2037
24.6430
βxxy
βxyy
βyyy
βxxz
βxyz
βyyz
βxzz
βyzz
βzzz
β0
β0
-10.5200
-20.2928
420.3295
336.6585
1486.4834 a.u
-30
12.84 ×10 esu

ACCEPTED MANUSCRIPT
(a)
(b)
Fig.1 The ORTEP plot (a) and optimized molecular structure (b) of DTPD.

ACCEPTED MANUSCRIPT
Fig. 10 The molecular structure with molecular axis representation of DTPD.