Sulphonamide chalcones: Conformationally diverse yet optically similar

Article abstract of DOI:10.1016/j.molstruc.2019.126896

In this paper, we present the synthesis of three chalcone analogues and their spectroscopic, structural and optical characterization. The influence of the different substituents on the crystalline structure and on their optical properties was evaluated. T

Full text of DOI:10.1016/j.molstruc.2019.126896

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Sulphonamide chalcones: Conformationally diverse yet optically similar
Jean M.F. Custodio, Fernando Gotardo, Wesley F. Vaz, Giulio D.C. D'Oliveira,
Leandro H.Z. Cocca, Ruben D. Fonseca, Caridad Noda Perez, Leonardo de Boni,
Hamilton B. Napolitano
PII:
S0022-2860(19)30987-1
DOI:
https://doi.org/10.1016/j.molstruc.2019.126896
MOLSTR 126896
Reference:
To appear in: Journal of Molecular Structure
Received Date: 8 May 2019
Revised Date: 1 July 2019
Accepted Date: 2 August 2019
Please cite this article as: J.M.F. Custodio, F. Gotardo, W.F. Vaz, G.D.C. D'Oliveira, L.H.Z. Cocca,
R.D. Fonseca, C.N. Perez, L. de Boni, H.B. Napolitano, Sulphonamide chalcones: Conformationally
diverse yet optically similar, Journal of Molecular Structure (2019), doi: https://doi.org/10.1016/
j.molstruc.2019.126896.
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2019 Published by Elsevier B.V.

Sulphonamide Chalcones: Conformationally Diverse yet Optically
Similar
a
b
c
a
Jean M. F. Custodio *, Fernando Gotardo , Wesley F. Vaz , Giulio D. C. D’Oliveira , Leandro H.
b
bd
a
b
Z. Cocca , Ruben D. Fonseca , Caridad Noda Perez , Leonardo de Boni and Hamilton B.
c
Napolitano *
a
Instituto de Química, Universidade Federal de Goias, Goiania, Goias, Brazil
b
Instituto de Física de São Carlos, Universidade de São Paulo, Sao Paulo, Sao Paulo, Brazil
c
Ciências Exatas e Tecnológicas, Universidade Estadual de Goiás, Anapolis, Goias, Brazil
d
Campus Universitario, Universidad Popular del Cesar, Barrio Sabana, Valledupar, Colombia
Correspondence email: jeanmfcustodio@gmail.com; hbnapolitano@gmail.com
Synopsis Three sulphonamide chalcones are characterized. Comparisons between the substitution
patterns and optical properties are made.
Abstract
In this paper, we present the synthesis of three chalcone analogues and their spectroscopic,
structural and optical characterization. The influence of the different substituents on the
crystalline structure and on their optical properties was evaluated. The effects of derivatization
on the chalcones, both at the molecular and supramolecular levels, were evaluated. Also, the
molar absorptivity, the first hyperpolarizability β and the two-photon absorption cross-section
σ2PA were obtained. The extended structures in each compound are stabilized by hydrogen-
bonded dimers and by a pseudo-ring formed from an intramolecular H-bond. It was observed
that more voluminous substituents, such as chlorine, contribute to the deviation from planarity.
Although many effects were observed in molecular structures of these analogues when in solid
form, experimental results of linear and nonlinear optical (NLO) properties showed that the
optical properties were not as much influenced in solution. In addition, and to support some
experimental results, the theoretical first hyperpolarizability was calculated and showed good
agreement with experimental results, which are approximately 10 × 10ꢀꢁꢂꢃꢃꢄꢅ /ꢇꢈꢉ.
ꢆ

Keywords: crystal structure; sulphonamide chalcones; optics properties
1. Introduction
Chalcones are a class of natural compounds with easy synthesis that have been
1
–5
extensively studied, showing to be promising compounds for diverse applications . Optically
active materials can be designed and improved from the combination of chalcones with other
6
–12
compounds that also have known application
. For example, the association of chalcones with
groups have formed new functional hybrid materials.
Among them, knowing the molecular structure of sulfonamide chalcones is important when
1
3,14
15
16,17
coumarins
, imino and indole
1
8–20
considering their biological applications
chalcones appears in just a few papers
materials is also scarce.
. The crystallographic description of sulfonamide
and reports of their application as functional
2
1–25
There are some examples regarding how structural modifications affect optical
properties. Gu and coworkers reported a proportional increase between NLO properties and the
2
6
electron donor strength . According to da Silva and coworkers, the presence of inter and
intramolecular interactions in chalcone co-crystals improves the second harmonic generation
2
7
efficiency . Also, the relationship between hyperpolarizability values and structural
modifications of a chalcone set was studied: the lowest values were found for less conjugated
and dimeric systems, while the highest values were found for compounds with strong electron
2
8
acceptors .
In this sense, we sought to determine if there are structural modifications in
sulphonamides chalcones that also retain their NLO properties. This paper presents synthesis,
crystallographic analysis and optical properties determination of three new hybrid chalcone
derivatives consisting of chalcone backbone linked with a sulphonamide group. The three
compounds synthesized are: (E)-3-(2-chlorophenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-
en-1-one (II), (E)-3-(2-fluoro-phenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (III)
and
(E)-3-(4-fluorophenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one
(IV).
Considering the different medium of crystal structure determination (solid state) and optical
properties (DMSO solution), we also simulated the conformations of II, III and IV in DMSO
2

medium. Finally, the influence of the substitutions was evaluated against on their crystal
structures and, in solution, on their optical properties, such as one- and two-photon absorption
spectra and molecular second harmonic generation. Crystallization process of these type of
compounds gives the possibility of optical second harmonic generation organic crystals to be
2
9–31
employed at the VIS-NIR region, which is the adequate region for optical communications
2. Experimental and computational procedures
2.1. Synthesis and Crystallization
2.1.1. General procedures
Compound 2’N-phenylsulfonyl acetophenone I was synthesized by reaction between
benzenesulfonyl chloride and 2-aminoacetophenone in dichloromethane, following literature
3
2
methods . Three 2-N’-sulfonamide chalcones were synthesized (compounds II to IV) by means
of Claisen-Schmidt condensation between the I and a substituted benzaldehyde via basic
catalysis in ethanolic medium.
2.1.2. Characterization
1
13
H NMR and C NMR spectra were recorded by a 400 MHz Bruker Avance III 11.75 T
NMR spectrometer. UV-Vis absorption spectra were recorded with a PerkinElmer Frontier Dual
Range. FT-IR spectrum was measured in Attenuated Total Reflectance mode in a Spectrum
Frontier equipment. Mass spectrometric analyses were performed using a MicrOTOF-Q® III
spectrometer equipped with a commercial ESI ion source (Bruker Daltonics, Bremen, Germany).
1
The degree of purity of the compounds was determined from the H NMR spectrum, by peak
area integration assigned to the structure and the total area of all peaks attributed to the material
under analysis. Absorption and fluorescence spectra were measured in the UV-vis-NIR region by
using, respectively, a SHIMADSZU UV-1800 and HITACHI F7000 fluorimeter. For both
measurements, a 10 mm optical path length fused silica cuvette was filled with sample solution.
-5
Chromospheres were dissolved in Dimethyl Sulfoxide (DMSO) in a concentration of about 10
mol/L.
3

2.1.3. Synthesis and physicochemical characterization
The synthesis and physicochemical characterization of compound, 1-(2-(phenylsulfonyl-
amine)phenyl)ethanone (I) and, (E)-3-(2-chlorophenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-
33
one (II), was reported by Demetrius and coworkers . The synthesis and physicochemical characterization
of compounds III and IV are described below. Claisen-Schmidt condensation reaction between
compound I and 2-fluorobenzaldehyde (III) and 4-fluorobenzaldehyde (IV) was used to synthes
compounds III and IV.
The synthesis of (E)-3-(2-fluorophenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-
one (III) was performed using 20.0 mmol of intermediate I, 22.0 mmol of 2-fluorobenzaldehyde
and 28.0 mmol of potassium hydroxide as catalyst. The reagents were dissolved in 200 mL of
ethanol and stirred at room temperature. After 2.5 h, the reaction was quenched by addition of
3
7% (w/w) hydrochloric acid in equimolar amounts to potassium hydroxide. The solution was
filtered, the precipitate suspended in solution of ethanol and water, and extracted with
dichloromethane. The non-aqueous phase was dried with sodium sulfate and allowed to
evaporate for crystallization. The crystals were collected and rinsed with ethanol. Yield 54.2 %
o
1
of a yellow crystalline solid, degree of purity: 97%, mp 136 – 138 C. H NMR (CDCl ) δ 7.15
3
(m, 2H); δ 7.21 (t, J 7.60 Hz, 1H); δ 7.40 (m, 4H); δ 7.46 (d, J 15.85 Hz, 1H); δ 7.50 (t, J 7.65
Hz, 1H); δ 7.58 (t, J 7.63 Hz, 1H); δ 7.75 (d, J 15.80 Hz, 1H); δ 7.76 (d, J 8.25 Hz, 1H); δ 7.83
1
3
(
(
(
m, 3H); δ 11.17 (s, 1H) (Fig. S3); C NMR (CDCl ) δ 116.41 (d, J 21.99 Hz), 120.81, 122.60
3
d, J 11.31 Hz), 123.24, 124.670 (d, J 3.11 Hz), 124.673 (d, J 12.70 Hz), 127.24, 129.00, 130.00
d, J 2.58 Hz), 130.73, 132.33 (d, J 8.90 Hz), 132.88, 134.48, 138.71, 139.38, 139.94, 161.79 (d,
J 255.01 Hz) (Fig. S4), 192.86; IR 1645 (m), 1491 (m), 1331 (m), 931 (m), 756 (s); HRMS
+
+
calculated for [C H FNO S+H] = 382.0913, found 382.0727; [C H FNO S+Na] 404.0733,
2
1
16
3
21 16
3
found 404.0553.
The synthesis of (
E)-3-(4-fluorophenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-
2-en-1-one (IV) was performed employing 20.0 mmol of intermediate
I
, 21.7 mmol of 4-
flu-orobenzaldehyde and 28.0 mmol of potassium hydroxide dissolved in 200 mL of
ethanol and stirred at room temperature. After 4.5 h of stirring, the reaction was quenched
by addition of 37% (w/w) hydrochloric acid in equimolar amounts to potassium
hydroxide. The solution was filtered, the precipitate suspended in solution of ethanol and
water, and extracted with dichloromethane. The dichloroethane phase was dried with
4

sodium sulphate and allowed to slowly evaporate for crystallization. The crystals were
collected and rinsed with ethanol. Yield, 3.30 g (43.3%) of a yellow crystalline solid,
o
1
3
degree of purity of 97%, mp 136 – 139 C. H NMR (CDCl ) δ 7.12 (m, H); δ 7.28 (d, J
3
1
1
1
5.55 Hz, H); δ 7.39 (m, 2H); δ 7.44 (m, H); δ 7.49 (ddd, J 1.46 Hz, 7.26 Hz, 8.46 Hz,
1
2
1
1
H); δ 7.60 (m, H); δ 7.65 (d, J 15.55 Hz, H); δ 7.75 (dd, J 0.67 Hz, 8.38 Hz, H); δ 7.83
3
1
13
(
m, H); δ 11.20 (s, H) (Fig. S5); C NMR (CDCl
3
) δ 116.30 (d, J 21.78 Hz), 120.67,
1
1
1
21.75 (d, J 2.25 Hz), 123.16, 124.66, 127.26, 129.00, 130.57 (d, J 8.79 Hz), 130.58,
30.72 (d, J 3.24 Hz), 132.88, 134.42, 139.46, 139.93, 144.68, 164.33 (d, J 252.57 Hz),
92.56 (Fig. S6); IR 1645 (m), 1495 (m), 1332 (m), 930 (m), 744 (m); HRMS calculated
+
+
for [C H FNO S+H] = 382.0913, found 382.0798; [C H FNO S+Na] 404.0733,
21
16
3
21 16
3
found 404.0628.
2
.2. Crystallographic characterization
The single crystals selected for crystallographic characterization were obtained by
evaporation of dichloromethane in ambient atmosphere for compound II and for compounds III
and IV the evaporation of the dichloromethane in an atmosphere rich in ethyl ether was the
methodology used to obtain the crystals. The single crystals were mounted in a Bruker APEX II
CCD diffractometer with graphite-monochromator MoKα radiation (λ = 0.71073 Å). Data were
measured at room temperature. Structure solutions were determined by Direct Methods using
3
4
2
SHELXS software and were refined by full-matrix least squares on F using SHELXL2014
3
5
software . All hydrogen atoms were placed in calculated positions and refined with fixed
individual displacement parameters [U (H) = 1.2 or 1.5 U (C)] according to the riding model
iso
eq
(C–H bond lengths of 0.97 and 0.96 Å for aromatic and methyl groups, respectively). Finally, the
3
6
37
chemical parameters were validated by means of Platon and Parst programs throughout the
3
8
39
38
WingX suite . Tables and figures were generated by using Mercury and ORTEP programs.
Molecules II, III and IV were deposited in the Cambridge Crystallographic Database Centre
(CCDC) under codes 1868826, 1868827 and 1868828, respectively. Using the software
Gaussian, the conformations of II, III and IV were simulated for DMSO medium and they were
found to be similar, so that the crystal structural properties can be extended to the aqueous
medium.
5

2.3. Nonlinear optical measurements
2.3.1. Two-Photon Absorption
Two-photon absorption (2PA) cross section spectra were determined by employing
4
0
tunable femtosecond Z-Scan technique . This technique allows the quantification of the 2PA
cross section by monitoring the sample transmittance. The sample is translated along (z-
direction) a focused intense laser beam. Changes in the optical transmittance are acquired as a
function of the sample position (Z). Consequently, around the focus, the transmittance of the
laser by the sample decreases proportionally to the induced 2PA. Further from the focal region,
the laser intensity diminishes and the nonlinear optical effects (2PA) are not induced, resulting in
only linear optical transmittance. The ratio between the transmittance for each Z-position to the
transmittance away from the focus is defined as the normalized transmittance (T(z)), from which
4
0
the 2PA cross section can be evaluated by employing Eq. (1). Further details see: .
In our experimental setup, a tunable optical parametric amplifier (TOPAS), pumped by a
Ti:Sapphire (CPA-2001 system from Clark-MXR Inc.) laser with 150 fs pulse width at 775 nm,
operating at 1 kHz repetition rate is used. This device delivers tunable wavelengths from 470 nm
up to 2000 nm with 120 fs pulse width, operating at a 1 kHz repetition rate. The laser beam is
focused by a 15 cm convergent lens at the Z-Scan experimental setup. The sample is positioned
and translated with respect to the focused beam, and the transmitted light is registered by a
Silicon photodetector for each Z-position of the sample. The signal is amplified and averaged by
a commercial locking amplifier in order to increase the signal/noise ratio. Once the normalized
transmittance Z-Scan signature is obtained, the 2PA cross section is determined by fitting T(Z) to
4
0
Eq. 1 :
ꢌ
ꢔ
ꢒꢓ
ꢀ
TꢊZꢋ = √ꢍꢎ
ꢑ
ln ꢃ[ 1 + q ꢊZ, 0ꢋe ]dt (1).
ꢂ
ꢀꢔ
ꢊꢐ,ꢂꢋ
ꢏ
ꢗ
ꢗ ꢀꢌ
The sample position is defined by ꢕ,ꢃꢖ is given by ꢖ = α I ꢚꢃꢊ1 + Z /Z ꢋ . I ꢃis
ꢂ
ꢂ
ꢗꢘꢙ ꢂ
ꢂ
ꢂ
the pulse intensity, Z is the Rayleigh length and, finally, ꢚ is the sample optical path. 2PA cross
ꢂ
section is defined by σꢗꢘꢙ = ꢊℏω/Nꢋαꢗꢘꢙ , in which αꢗꢘꢙ is the nonlinear absorption
6

coefficient,ꢃℏ is the Planck constant, ω is the light frequency, and N is the number of molecule
per cm . To quantify the σꢛꢘꢙ, we usually use 1ꢃGM = 1 × 10ꢀꢆꢂꢃcm ꢃsꢃphoton (Göppert-
3
ꢜ
ꢀꢌ
4
1
Mayer unit (GM); . This procedure was performed at different wavelengths in order to obtain
the 2PA spectrum of each sample.
2.3.2. First order hyperpolarizability
4
2
To determine the first hyperpolarizability (β) of each chalcone , we employed the Hyper
4
2,43
Rayleigh scattering (HRS) technique
. For this, we use a Nd:YAG Q-Switched mode-locked
laser with pulses at 1064 nm (ω). This configuration delivers an envelope about 300 ns which
contains of about 30 pulses of 100 ps, these pulses in the envelope are separated by 13.2 ns from
4
3
each one . Laser was set to operate at 100 Hz of repetition rate. Pulses are focalized at the
samples and the scattered optical second harmonic at 532 nm (2ω) was collected by a
photomultiplier tube positioned perpendicular to the incident beam (1064 nm). It is important to
highlight that we used an optical filter centered at 532nm with 10 nm of bandwidth at the
photomultiplier window to ensure that only the nonlinear scattered signal is detected by the
photomultiplier. The second harmonic scattered signal Iꢊ2ωꢋ is related to the laser intensity Iꢊωꢋ
by the following expression:
ꢝꢊ2ꢞꢋ = ꢟ ∑ꢢ ꢠ ꢤ ꢝ ꢊꢞꢋ
ꢗ ꢗ
(2).
ꢡꢣꢌ
ꢡ
ꢡ
In this equation, ꢠ is the molecular concentration, G is a constant instrumental factor. G
ꢡ
depends on the laser beam and experimental setup and can be determined using a sample with a
known β value; in this case, we use para-nitroaniline (pNA) dissolved in DMSO,
βꢊ1064ꢃnmꢋ = 25.3 × 10ꢀꢁꢂcm /esu . It is important to emphasize here that chalcones and
ꢆ
43
pNA were dissolved in high concentration in DMSO solvent. Thus, it was possible to determine
β of the three chalcone derivatives measuring Iꢊ2ωꢋ for several N . A linear relation between
ꢥ
Iꢊ2ωꢋ and ꢠ is obtained, and the angular coefficient of it, αꢦꢧꢨꢩꢦꢪꢫꢬ, is related to βꢦꢧꢨꢩꢦꢪꢫꢬ by
ꢡ
E.q 3
7

ꢰꢱꢲꢳꢴꢱꢵꢶꢷ
ꢰꢸꢹꢺ
ꢗ
βꢦꢧꢨꢩꢦꢪꢫꢬ = β
(3)
ꢭ
ꢮꢯꢙ
in which, αꢦꢧꢨꢩꢦꢪꢫꢬ = Gβꢗ
and αꢮꢯꢙ = Gβꢗ
.
ꢮꢯꢙ
ꢦꢧꢨꢩꢦꢪꢫꢬ
3
. Results and discussion
.1. Molecular Structure of Compound II
The compound II is a chalcone with a chlorine atom and phenyl-sulfonamide group
3
ortho-bonded to aromatic rings A and B, respectively (Fig. 1a). It crystallizes in the monoclinic
centrosymmetric space group P2 /c (Table 1). The angle formed by the mean plane of the
1
chalcone rings A and B is 42.59(5)°, demonstrating a significant deviation from co-planarity.
This is supported by the Cl1–C1–C9–O1 dihedral angle ω1 = 31.07(13)°, which shows a
synclinal conformation of the chlorine group with respect to carbonyl group.
8

Figure 1 50% probability ellipsoid plot of II (a), III (b) and IV (c). Non-hydrogen atoms are arbitrarily
labelled, and hydrogen atoms are shown as spheres of arbitrary radii.
Table 1 Experimental details
(
II)
(III)
(IV)
Crystal data
Chemical formula C H ClNO S
C H FNO S
C H FNO S
2
1
16
3
21 16
3
21 16
3
Mr
397.86
381.41
381.41
Crystal system,
space group
Monoclinic, P2
1
/c
Monoclinic, C2/c
1
Monoclinic, P2 /c
Temperature (K)
296
296
296
a, b, c (Å)
13.7952 (7), 7.5840 (4),
0.2728 (9)
62.896 (3)
26.984 (3), 7.6486 (8), 18.354 13.1059 (5), 17.5044 (8),
2
(2)
8.1948 (4)
β (°)
107.479 (3)
102.278 (2)
9

3
V (Å )
1888.07 (17)
3613.2 (7)
1836.98 (14)
Z
4
8
4
Radiation type
Mo Kα
0.33
Mo Kα
Mo Kα
−1
µ (mm )
0.21
0.21
Crystal size (mm) 0.74 × 0.46 × 0.34
Data collection
0.10 × 0.10 × 0.08
0.65 × 0.22 × 0.21
Diffractometer
Bruker APEX-II CCD
Bruker APEX-II CCD
Bruker APEX-II CCD
Absorption
correction
–
–
–
No. of measured,
independent and
observed [I > 2σ(I)]
reflections
27435, 3880, 3394
24691, 3749, 2712
23587, 3762, 2982
R
int
0.035
0.626
0.054
0.630
0.033
0.626
−1
(
sin θ/λ)max (Å )
Refinement
2
2
R[F > 2σ(F )],
0.038, 0.106, 1.04
3880
0.045, 0.132, 1.06
0.040, 0.110, 1.04
2
wR(F ), S
No. of reflections
3749
256
3762
263
No. of parameters 259
H-atom treatment H atoms treated by a mixture of H atoms treated by a mixture H atoms treated by a mixture
independent and constrained
refinement
of independent and
constrained refinement
of independent and
constrained refinement
−
3
ꢀ
ρmax, ꢀρmin (e Å ) 0.27, −0.33
0.30, −0.31
0.32, −0.28
Computer programs: SHELXL2016/6 (Sheldrick, 2016).
Only C–H⋯O intermolecular interactions are observed stabilizing the crystal packing of
ꢗ
II. Two molecules are assembled in a dimeric arrangement by a ꢻ ꢊ18ꢋ motif involving
ꢗ
carbonyl group and aromatic ring C (Fig. 2a). These dimers are joined together by means of a
bifurcated interaction which an Osulfonyl atom serves as an acceptor from two carbon atoms in a
ꢌ
ꢌ
ꢼ
ꢊ8ꢋ[ꢻ ꢊ6ꢋ] motif (Fig. 2b). Finally, the supramolecular arrangement of II is stabilized by one
ꢗ
ꢗ
more C–H⋯O interaction involving the sulfonyl group and the aromatic ring A in a ꢼ(11) motif
giving rise to a 1D chain running parallel to [001] (Table 2).
1
0

Figure 2 Dimer formed by two molecules II (a) and its crystal packing (b)
Table 2 Hydrogen-bond geometry (Å, º) for (II)
D—H···A
D—H
H···A
D···A
D—H···A
137.1 (16)
144.1 (17)
118.1 (15)
128.5 (16)
i
C5—H5···O3
0.95 (2)
0.92 (2)
0.98 (2)
0.94 (2)
2.58 (2)
2.53 (2)
2.70 (2)
2.59 (2)
3.342 (2)
3.320 (2)
3.274 (2)
3.255 (2)
ii
C21—H21···O1
C12—H12···O2
C13—H13···O2
iii
iii
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2.
3.2. Substituent effect on the crystal structure
We evaluated substitution effects by comparing the crystal structures of II and III, which
differs only by the atom bonded to the ring A. Compound III substitutes fluorine for the chlorine
atom in II (Fig. 1b). III crystallizes in the C-centered monoclinic space group C /c (Table 1).
2
Figure 3 shows a molecular overlay obtained by mapping the aromatic ring B from molecules II
and III. The main structural difference is the planarity of the chalcone moiety. For III, the angle
formed between aromatic rings A and B is smaller than II (∡ = 20.37(10)°), as result of
reduction of steric repulsion between the fluorine and carbonyl group and n⋯π donation
differences of fluorine and chlorine atoms. Since chlorine atom has a greater atomic radius, this
4
4
repulsion is greater in II .
1
1

Figure 3 Overlapping obtained by fixing the aromatic ring B from molecules II (cyan color) and III
blue color).
(
Similar to II, the crystal packing of III is also composed by dimers (Fig. 4). There is a
ꢗ
dimer with ꢻ ꢊ16ꢋ motif (blue color, in Fig. 4) involving sulfonyl group and olefinic hydrogen.
ꢗ
ꢜ
A 1D chain is formed by assembling these dimers in a second order ꢻ ꢊ16ꢋ ring motif (pink
ꢜ
color, in Fig. 4) parallel to [101]. The last C–H⋯O interaction observed in the crystal packing of
III involves the carbonyl group and the aromatic ring C and contributes to 3D arrangement of III
(Table 3).
Figure 4 Crystal packing of III, evidencing the supramolecular arrangement composed by two dimers
ꢗ
ꢗ
with ꢻ ꢊ16ꢋ ring motif (blue) joined by a ꢻ ꢊ16ꢋmotif (pink)
ꢗ
ꢗ
1
2

Table 3 Hydrogen-bond geometry (Å, º) for (III)
D—H···A
D—H
H···A
D···A
D—H···A
156 (3)
169 (2)
163 (2)
121 (2)
i
C3—H3···O2
C5—H5···O3
C8—H8···O3
0.95 (3)
0.97 (3)
0.96 (3)
0.88 (3)
2.69 (3)
2.51 (3)
2.55 (3)
2.73 (3)
3.577 (3)
3.466 (3)
3.475 (3)
3.273 (3)
ii
ii
iii
C20—H20···O1
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+1/2, −y+3/2, −z; (iii) −x+1/2, y−1/2, −z+1/2.
3.3. Positional effect on the crystal structure
The positional effect is evaluated by comparing the crystal structures of III and IV,
which differs only by the position of the atom bonded to aromatic ring A. Similarly to III, the
structural isomer IV also has a fluorine atom bonded to the aromatic A, but in the para position
(
Fig. 1c). It crystallizes in the primitive monoclinic space group P2 /c (Table 1).
1
Structural differences between III and IV are demonstrated in Figure 5. Compound IV
has a more planar chalcone moiety than compound III, as confirmed from the angle formed by
its aromatic rings A and B (∡ = 3.32°). This difference is again from a reduction of the electron-
electron repulsion of fluorine atom and carbonyl group. Since III has an ortho-bonded fluorine
4
4
atom, this repulsion is stronger than in IV, causing the deviation from planarity .
Figure 5 Overlapping obtained by fixing the aromatic ring B from molecules III (blue color) and IV
(
gray color).
1
3

Carbonyl group and aromatic ring C are assembled into centrosymmetric dimers with
ꢻ
ꢗꢗ ꢊ20ꢋ motif (Fig. 6a). Also observed is a 1D chain formation involving the aromatic ring B and
the sulfonyl group in a ꢼꢊ11ꢋ motif running along [010]. These chains are assembled in a 3D
arrangement by means of Caromatic–H⋯Osulfonyl and Caromatic–H⋯Osulfonyl interactions (Fig. 6b);
(Table 4).
Figure 6 Dimer formed by two molecules IV (a) and its crystal packing (b)
Table 4 Hydrogen-bond geometry (Å, º) for (IV)
D—H···A
D—H
H···A
D···A
D—H···A
129.2 (19)
174 (2)
i
C20—H20···O1
0.94 (3)
0.92 (3)
0.94 (3)
0.93 (3)
2.64 (3)
2.67 (3)
2.71 (3)
2.64 (3)
3.317 (3)
3.590 (2)
3.416 (2)
3.375 (3)
ii
C5—H5···O2
iii
C20—H20···O3
132.3 (19)
136.0 (19)
iv
C19—H19···F1
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, y+1/2, −z+1/2; (iii) x, y, z−1; (iv) x−1, −y+1/2, z−1/2.
3.4. One-, two-photon absorption spectra and first order hyperpolarizabilities
Figure 7 shows molar absorptivity (dashed blue lines) of the three chalcone derivatives
dissolved in DMSO solvent at room temperature. One can see that the lower transition band is
-
1
-1
located at approximately 318 nm with a molar absorptivity of about 16500 L mol cm to the
-
1
-1
derivatives shown in (a) and (c) and about 19500 L mol cm for (b). Changes in the atoms, from
chlorine to fluorine and from ortho to para position, did not significantly change the energy of the
1
4

lowest energetic band and the molar absorptivity magnitude, when comparing the compounds. All
three compounds dissolved in DMSO are transparent at wavelengths longer than 400 nm.
Fluorescence emission was not evidenced for these samples, which indicates a nonradiative
4
5
relaxation process from first singlet excited state to the ground state .
Figure 7 Linear absorption (ε) (dashed blue lines) and two-photon absorption (open red circles) spectra
of all three chalcone derivatives dissolved in DMSO solvent. The black line is the adjustments obtained
with Sum-Over-States model. The inset shows the molecular structure of the derivatives.
1
5

Figure 7 also depicts 2PA spectra (open red circles) of all three chalcones obtained
with fs-tunable Z-Scan technique. Each point of the spectrum represents the two-photon
absorption cross section calculated from Eq. (1). Similar to the 1PA spectrum, 2PA
spectra are not significantly different across the compounds. The maximum 2PA cross
sections are of the same order of magnitude. For all compounds, two 2PA bands appear
located at approximately 565 nm and 635 nm. The latter corresponds to the same
transition allowed by 1PA (~ 318 nm). The other, located at 565 nm, represents a state
located at approximately 255 nm, which has no similar 1PA. For wavelengths shorter than
5
00 nm, the 2PA cross sections increase due to the one-photon resonance enhancement.
Similarities in the 1PA and 2PA between the compounds could be understood by the
molecular structures. The chalcone moiety, which has the same -conjugated
ꢽ
characteristics, is responsible for the one- and two-photon absorption bands centered at
approximately 318 nm (636 nm) in all compounds. The replacement of the chlorine atom
to the fluorine, which has the higher electronegativity, do not affect considerable the 1PA
and 2PA spectra between the molecules.
It is important to mention here than by using both 1PA and 2PA spectra combined,
we could estimate information about the magnitude of some electronic properties, such as
the transition dipole moments and permanent dipole moment difference between the
ground and first excited states
ꢊΔ
ꢾ
μ
ꢿ
=
ꢾ
μ
ꢿ
− ꢾμꢿ ꢂꢂꢋ . For example, the transitions dipole
ꢂꢌ
ꢌꢌ
46
moment from the ground to the first excited state (μꢂꢌ) is determined by :
ꣀ
ꢁ
∙ꢌꢂ ꢩꢫ
ꢊ
ꢌꢂ
ꢋ
ħꢦ ꢫ
ꣃꢓ
μꢂꢌꢗ
=
ε ω
ꢊ ꢋ
dω
(4),
ꢑ
ꢊ
ꢗꢍꢋꣀꢯ ꣁ
ꢺ
ꢏꣂ
in which, Nꢙ is Avogadro’s number, ħ is Planck’s constant, c is the speed of light, and
ꢗ
ꢗ
ωꢂꢌ represents the transition frequency of the first excited state. L = 3n ⁄ꢊ2n + 1ꢋ
describes the Onsager local field factor, which represents the surround medium effect of
47
the solvent to the solute , that in the present work is DMSO solvent, with a refractive
index (n) equal to 1.42. In Equation (4), ꣄ꢊꢞꢋ is the molar absorptivity, obtained from the
linear absorption measurements.
1
6

Combining μ , determined directly from the linear absorption spectrum, with
ꢂꢌ
some other spectroscopic parameters, the experimental 2PA spectrum can be modeled
with Sum-Over-States (SOS) approach. In Figure 7, the solid black lines represent a
construction of the experimental 2PA (open circles) with SOS model, which is given by
48,49
the following expression
:
ꢌꢗ꣇ ꢍ꣈
ꣁꢓ
|꣌ꢏꣂ|ꢓ꣍꣌ ꣊ꢏꣂ
ꢓ
ꢓ
ꢓ
ꢓ
ꢓ
|꣌ꣂꢓ| |꣌ | ꣊
ꢏꣂ
|꣌ꣂꣀ| |꣌ | ꣊
ꢏꣂ
ꣅ
꣆ꣅ
Lꢜ
ꢏꣂ
ꢏꢓ
ꢓ
ꢏꣀ
ꢓ
σ
ꢊωꢋ =
꣋
+
+
꣎
(5)
ꢗꢘꢙ
ꢊꢦꢧꢫꢋꢓ
ꢓ
ꢓ
ꢓ
ꢓ
ꢓ
ꢓ
ꢆ
ꢊꣁꢏꣂꢀꣁꢋ ꣉꣊
ꢊꣁꢏꣂꢀꢗꣁꢋ ꣉꣊
ꢊꣁꢏꢓꢀꢗꣁꢋ ꣉꣊
ꢊꣁꢏꣀꢀꢗꣁꢋ ꣉꣊
ꢏꣂ
ꢏꣂ
ꢏꢓ
ꢏꣀ
in which, ω is the frequency of the laser. ωꢂꢫ and Γ are, respectively, the transition frequency
ꢂꢫ
and damping constant of the 0 → n transition (n=1,2,3). It is important to mention here that the
three terms, inside of the brackets, describe the electronic transitions observed in the 2PA
experimental spectrum. In all terms, one can notice the product between the dipole moments in
the numerator, in which all have μꢂꢌ in common, an input parameter obtained from the linear
absorption spectra. It ensures that each term in the brackets is independent and only one dipole
parameter is adjusted per term. In summary, Table 5 presents the parameters obtained with both
1
PA and 2PA spectra combined with Eq. 4 and Eq. 5. The damping constants were used to be
Γꢂꢫ = 0.3 eV, which is common, in most cases, to describe electronic transitions for organic
molecules at the UV-VIS region. These parameters are close in magnitude, which indicates that
the charge distribution at the ground and excited state are similar between the molecules.
Values in Table 5 and the magnitude of the 2PA cross section shown in Figure 7,
taking in consideration the experimental error, are close to those reported in the literature
for chalcone-based compounds, which were obtained by using similar methodology of
45,50–53
measurements
. Values in Table 5 and the magnitude of the 2PA cross section
shown in Figure 7, taking in consideration the experimental error, are close to those
reported in the literature for chalcone-based compounds, which were obtained by using
45,50–53
similar methodology of measurements
, as the ones employed in the present work.
For example, ref. 48 presents a similar study in two substituted chalcones employing
similar fs Z-Scan experiment to determine the 2PA cross-sections. Results have shown
similar 2PA cross-sections between the chalcone molecules. The magnitudes observed for
1
7

the 2PA cross-section in the lower energetic band are close (~ 15 GM) to the ones showed
here. It is interesting to point out that the 2PA band located at 565 nm for molecules II
,
III and IV, have no similar band in the case of Ref. 48. One explanation for it is the
presence of the phenylsulfonylamine group attached to the main chalcone moiety in our
X
molecules. Santos at al. studied two-photon absorption spectrum in bromo- and chloro-
derivatives of dibenzylideneacetone and obtained a maximum value of about 25 GM for the
5
1
molecule containing bromine and 17 GM for the one with chlorine atom. Lemes et al.
presented a similar study in a chalcone derivative with a chlorine atom in the para position
and also with twice the conjugation length when compared to our molecules. In that work, a
maximum 2PA cross-section of about 30 GM was observed. The increase in the 2PA magnitude
comparing to the present molecules is explained by the conjugation length be greater. Custodio
5
2
et al studied two-photon absorption spectrum of a bromine sulfonamide chalcone , with a
similar molecular structure to the ones presented here. 2PA maximum cross-section value of 10
GM was obtained for the lower energetic band. A blue shifted in the one- and two-photon
absorption spectrum is observed when compared to the sulphonamide chalcone presented here. It
can be understood by the presence of bromine atom, which is less electronegative than chlorine
and fluorine atoms. Moreover, it is important to describe that for bromine sulfonamide
chalcone, the overlap between the two 2PA bands have increased. It indicates that charge
distribution in the phenylsulfonylamine group attached to the main chalcone moiety may not
suffer influence replacing bromine by chlorine or fluorine atoms.
Table 5 Transitions dipole moments and permanent dipole moment difference for the three compounds
studied in this work, in Debyes unit.
Chalcone derivatives
II
III
IV
μꢂꢌ Δμꢂꢌ μꢌꢗ
μꢌꢁ
4.0
4.5
4.5
6.4
7.2
6.5
4.6
3.8
5.2
4.0
4.1
4.4
Concerning to the molecular second harmonic generation measurements, which are
related to the first order hyperpolarizability (β) of the molecule, the values of chalcone
derivatives were determined after the experimental setup was calibrated with pNA
1
8

(
standard compound) dissolved in the same solvent. As it was shown in the molecular
structure, one can see that all three chalcones derivatives are noncentrosymmetrical
molecules in terms of charge distribution. It because of the different donor-acceptor
groups attached to the main chalcone moiety. Consequently, when the molecules are in
solution and not crystallized, it is expected to observe a very low incoherent second-order
signal from each individual molecule that can be measured by using HRS technique. The
measured scattered nonlinear signal (532 nm) shows a quadratic dependence with the
pump intensity (1064 nm), indicating that two photons of 1064 nm are annihilated in
order to generate one of 532 nm. It can be visualized at the left hand inset in Fig. 8, as
example, for compound III. The solid line, for each curve, represents the best second
ꢂ
order polynomial fit. Also, in Fig. 8, it is presented the linear dependence of Iꢀ2ωꢁ/I ꢀωꢁ
(
open symbols) as a function of five molecular concentrations for II, III, IV derivatives,
as well as pNA molecule. Lines in these graphs represent the best linear fits, in which the
angular coefficients, when compared with the pNA, provide β values for the studied
samples, all calculated from Eq. (3).
ꢂ
Figure 8 Linear dependence of Iꢀ2ωꢁ/I ꢀωꢁ as function of the molecular concentrations for pNA
(
squares) and chalcone derivatives: II (blue triangle), III (green triangle and IV (circles). Lines represent
the linear fits. The inset, at left side, represents the first hyperpolarizability scattering signals as a function
1
9

of the pump intensity for five distinct molar concentrations of sample III. Lines are the best second order
polynomial fits. Similar curves were obtained for the other compounds. The inset, at right side, depicted
the
β
values for all compounds and pNA.
The results obtained for all three compounds showed that values of β are similar to
-29
5
each other of approximately 1x10 cm /esu. This nonlinear optical effect agrees with the
other optical characteristics, such as linear absorption and 2PA spectra. In other words, as
can be seen, linear and 2PA spectra are all similar across all three chalcones analysed.
Consequently, it is expected that β´s are similar when comparing the three compounds
studied here. β values at 1064 nm for II, III and IV can be indirectly estimated by
54
employing a simplified two-level model , taking in consideration properties obtained
from the one- and two-photon absorptions. In this model, Δμꢂꢌ and μꢂꢌ (presented at Table
5
), were used in this approach to first determine the static first-order hyperpolarizability (β ) by
ꢂ
employing the following expression:
|꣌ꢏꣂ|ꢓ|꣍꣌ꢏꣂ
ꢊℏꣁꢏꣂꢋꢓ
|
ꢁ
ꢗ
βꢂꢊ0; 0,0ꢋ =
(6),
in which, ℏωꢂꢌ is the energy of the first electronic transition, in the present case to be
approximately 3.88 eV for all three compounds, because the lower electronic transition is at the
approximately same wavelength. The estimated static first-order hyperpolarizabilities are 7.3, 7.7
-30
5
and 8.5 x10 cm /esu, respectively, for compounds II, III and IV.
To calculate the dynamical β and thus compare to the experimental ones, one can take
into account the resonance enhancement effect due to the optical frequency dispersion, it can be
54–56
evaluated by using the undamped two-level model
. With this simplified model, the dynamic
hyperpolarizabilities of the compounds were extrapolated at the incident laser frequency (ꢞ),
5
4
which is far from the first excited state (ℏω ), by using :
ꢂꢌ
꣏
ꣁ
ꢏꣂ
βꢊ−2ω; ω, ωꢋ = ꣐ꣁꢓ
βꢂ
(7).
ꢀꢜꣁ ꣑꣐ꣁ ꢀꣁ꣒ꢓ꣑
ꢓ
ꢓ
ꢏꣂ
ꢏꣂ
In Figure 9, the experimental values obtained with the HRS technique (symbols)
are compared to the ones obtained with the undamped two-level model (solid lines), the
latter calculated by using 1PA and 2PA experiments. One can see a good agreement
2
0

between both results at approximately 1.16 eV (~ 1064 nm). At 1.16 eV, the values
-30
obtained with Eq. 7 are 12.6 (1.26 times higher), 13.3 (1.02 times higher) and 14.7 x10
5
cm /esu (1.47 times higher), respectively, for compounds II, III and IV.
Figure 9 Experimental HRS signal measured at 1064 nm (~ 1.16eV) (symbols) and simplified two-level
dispersion model (lines) for II, III and IV.
Values of the molecular optical second harmonic are in the same order of
45,50–53
magnitude to the ones found in the literature for chalcone-based compounds
. In
that works, a similar HRS experimental methodology was employed. For example,
4
8
Abegão et al determined values of the molecular second order nonlinear response of
about two times higher than the ones reported here, for two substituted chalcones
dissolved in methanol. Also, a chalcone derivative with a chlorine atom in the para position
−
30
5
and with twice the conjugation length showed a value of about 22 ×10 cm /esu, obtained also
5
1
52
at 1064 nm . Custodio et al determined for a bromine sulfonamide chalcone a value similar to
5
3
the ones presented here. Santos et al
studied bromo- and chloro-derivatives of
dibenzylideneacetone, in which the molecules presented a conjugation length longer than ours
chalcones. The results obtained for the molecular second-order nonlinear response were 25 and
−30
5
2
7 ×10
cm /esu respectively for bromine and chlorine dibenzylideneacetone. The results
2
1

reported in the literature, by using similar methodology, have shown that chalcones molecules
present similar values of first order hyperpolarizability. An augment of β magnitude can be
understood by an increase in the conjugation length of the molecule associated to the presence of
donor-acceptor groups, which defined a noncentrosymmetric charge distribution.
4. Conclusions
The substituent effect on crystal structures was measured by comparison of molecules II
and III, which differ only by the atom bonded to the ring A. For III, the angle formed by
aromatic rings A and B was found to be smaller than II, evidencing the planarity deviation
observed due to the greater atomic radius of chlorine. In addition, the positional effect on the
crystal structure was evaluated after comparing the isomers III and IV. The para substitution
observed in IV contributed to the planarity of its chalcone backbone, due to its lower steric
repulsion when compared to III, a ortho-substituted chalcone. Finally, crystal packing of the
molecules was found to be stabilized by dimers and by a pseudo-ring formed from an
intramolecular H-bond. Although slightly different structural conformations were observed for
the molecules II, III and IV at solid state, experimental results from linear and nonlinear optical
measurements in solution showed that the values of optical effects are not significantly
influenced by these structural modifications. Considering the nonlinear optical properties,
estimated first hyperpolarizabilities (β´s), by employing parameters obtained from distinct
spectroscopic techniques, are in good agreement with the ones experimentally obtained with
Hyper Rayleigh scattering technique, which are approximately 10 × 10ꢀꢁꢂꢃꢃꢄꢅ /ꢇꢈꢉ.
ꢆ
5. Supporting Information
1
13
1
H and C{ H} NMR spectrum (500 MHz, CDCl ), of compounds II, III and IV.
3
Acknowledgements
The authors are grateful to Professor Allen Oliver for his collaboration in reading this
manuscript. The authors also acknowledge the financial support of the Conselho Nacional de
Desenvolvimento Científico e Tecnológico (CNPq), Fundação de Amparo à Pesquisa do Estado
2
2

de Goiás (FAPEG), INCT-FOTÔNICA, FAPESP 2016/20886-1 and 2018/11283-7, Army
Research Laboratory W911NF-17-1-0123 and Air Force Office of Scientific Research (FA9550-
1
2-1-0028). This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal
de Nível Superior - Brasil (CAPES) - Finance Code 001..
References
(
1)
Zhu, X.; Yin, F.; Zhao, H.; Chen, S.; Bian, Z. Some New Azobenzene Liquid Crystals Involving
Chalcone and Ester Linkages. RSC Adv. 2017, 7 (73), 46344–46353.
https://doi.org/10.1039/C7RA06958H.
(
2)
Tan, J.; Zhang, Y.; Zhang, M.; Tian, X.; Wang, Y.; Li, S.; Wang, C.; Zhou, H.; Yang, J.; Tian, Y.;
et al. Small Molecules of Chalcone Derivatives with High Two-Photon Absorption Activities in
the near-IR Region. J. Mater. Chem. C 2016, 4 (15), 3256–3267.
https://doi.org/10.1039/C6TC00382F.
(
3)
Ramaganthan, B.; Gopiraman, M.; Olasunkanmi, L. O.; Kabanda, M. M.; Yesudass, S.; Bahadur,
I.; Adekunle, A. S.; Obot, I. B.; Ebenso, E. E. Synthesized Photo-Cross-Linking Chalcones as
Novel Corrosion Inhibitors for Mild Steel in Acidic Medium: Experimental, Quantum Chemical
and Monte Carlo Simulation Studies. RSC Adv. 2015, 5 (94), 76675–76688.
https://doi.org/10.1039/C5RA12097G.
(
(
4)
5)
Gaur, R.; Gupta, V. K.; Pal, A.; Darokar, M. P.; Bhakuni, R. S.; Kumar, B. In Vitro and in Vivo
Synergistic Interaction of Substituted Chalcone Derivatives with Norfloxacin against Methicillin
Resistant Staphylococcus Aureus. RSC Adv. 2015, 5 (8), 5830–5845.
https://doi.org/10.1039/C4RA10842F.
Moura, N. M. M.; Núñez, C.; Faustino, M. A. F.; Cavaleiro, J. A. S.; Neves, M. G. P. M. S.;
Capelo, J. L.; Lodeiro, C. Preparation and Ion Recognition Features of Porphyrin–chalcone Type
Compounds as Efficient Red-Fluorescent Materials. J. Mater. Chem. C 2014, 2 (24), 4772–4783.
https://doi.org/10.1039/C3TC32496F.
(
(
6)
7)
Muhammad, S.; Xu, H.-L.; Zhong, R.-L.; Su, Z.-M.; Al-Sehemi, A. G.; Irfan, A. Quantum
Chemical Design of Nonlinear Optical Materials by Sp2-Hybridized Carbon Nanomaterials: Issues
and Opportunities. J. Mater. Chem. C 2013, 1 (35), 5439. https://doi.org/10.1039/c3tc31183j.
Moloney, J. V.; Newell, A. C. Nonlinear Optics. Phys. D Nonlinear Phenom. 1990, 44 (1–2), 1–
2
3

3
7. https://doi.org/10.1016/0167-2789(90)90045-Q.
(
8)
9)
G. Papadopoulos, Manthos, Sadlej, Andrzej J., Leszczynski, J. Non-Linear Optical Properties of
Matter; Papadopoulos, M. G., Sadlej, A. J., Leszczynski, J., Eds.; Springer Netherlands:
Dordrecht, 2006. https://doi.org/10.1007/1-4020-4850-5.
(
(
Schneider, T. Nonlinear Optics in Telecommunications; Advanced Texts in Physics; Springer
Berlin Heidelberg: Berlin, Heidelberg, 2004. https://doi.org/10.1007/978-3-662-08996-5.
10) Muhammad, S.; Irfan, A.; Shkir, M.; Chaudhry, A. R.; Kalam, A.; AlFaify, S.; Al-Sehemi, A. G.;
Al-Salami, A. E.; Yahia, I. S.; Xu, H.-L.; et al. How Does Hybrid Bridging Core Modification
Enhance the Nonlinear Optical Properties in Donor-π-Acceptor Configuration? A Case Study of
Dinitrophenol Derivatives. J. Comput. Chem. 2015, 36 (2), 118–128.
https://doi.org/10.1002/jcc.23777.
(
(
(
(
(
11) Muhammad, S.; Al-Sehemi, A. G.; Su, Z.; Xu, H.; Irfan, A.; Chaudhry, A. R. First Principles
Study for the Key Electronic, Optical and Nonlinear Optical Properties of Novel Donor-Acceptor
Chalcones. J. Mol. Graph. Model. 2017, 72, 58–69. https://doi.org/10.1016/j.jmgm.2016.12.009.
12) Muhammad, S.; Al-Sehemi, A. G.; Irfan, A.; Chaudhry, A. R. Tuning the Push–pull Configuration
for Efficient Second-Order Nonlinear Optical Properties in Some Chalcone Derivatives. J. Mol.
Graph. Model. 2016, 68, 95–105. https://doi.org/10.1016/j.jmgm.2016.06.012.
13) Mazzone, G.; Malaj, N.; Galano, A.; Russo, N.; Toscano, M. Antioxidant Properties of Several
Coumarin–chalcone Hybrids from Theoretical Insights. RSC Adv. 2015, 5 (1), 565–575.
https://doi.org/10.1039/C4RA11733F.
14) Wei, H.; Ruan, J.; Zhang, X. Coumarin–chalcone Hybrids: Promising Agents with Diverse
Pharmacological Properties. RSC Adv. 2016, 6 (13), 10846–10860.
https://doi.org/10.1039/C5RA26294A.
15) Custodio, J. M. F.; Santos, F. G.; Vaz, W. F.; Cunha, C. E. P.; Silveira, R. G.; Anjos, M. M.;
Campos, C. E. M.; Oliveira, G. R.; Martins, F. T.; da Silva, C. C.; et al. Molecular Structure of
Hybrid Imino-Chalcone in the Solid State: X-Ray Diffraction, Spectroscopy Study and Third-
Order Nonlinear Optical Properties. J. Mol. Struct. 2018, 1157, 210–221.
https://doi.org/10.1016/j.molstruc.2017.12.023.
(
16) Aneja, B.; Arif, R.; Perwez, A.; Napoleon, J. V.; Hasan, P.; Rizvi, M. M. A.; Azam, A.;
Rahisuddin; Abid, M. N-Substituted 1,2,3-Triazolyl-Appended Indole-Chalcone Hybrids as
Potential DNA Intercalators Endowed with Antioxidant and Anticancer Properties.
2
4

ChemistrySelect 2018, 3 (9), 2638–2645. https://doi.org/10.1002/slct.201702913.
(
17) Gupta, S.; Maurya, P.; Upadhyay, A.; Kushwaha, P.; Krishna, S.; Siddiqi, M. I.; Sashidhara, K. V.;
Banerjee, D. Synthesis and Bio-Evaluation of Indole-Chalcone Based Benzopyrans as Promising
Antiligase and Antiproliferative Agents. Eur. J. Med. Chem. 2018, 143, 1981–1996.
https://doi.org/10.1016/j.ejmech.2017.11.015.
(
(
18) Domínguez, J. N.; León, C.; Rodrigues, J.; Gamboa, N.; Domínguez, D. Synthesis and
Antimalarial Activity of Sulfonamide Chalcone Derivatives. Farm. 2005, 60, 307–311.
https://doi.org/10.1016/j.farmac.2005.01.005.
19) Eldehna, W. M.; Abo-Ashour, M. F.; Nocentini, A.; Gratteri, P.; Eissa, I. H.; Fares, M.; Ismael, O.
E.; Ghabbour, H. A.; Elaasser, M. M.; Abdel-Aziz, H. A.; et al. Novel 4/3-((4-Oxo-5-(2-
Oxoindolin-3-Ylidene)Thiazolidin-2-Ylidene)Amino) Benzenesulfonamides: Synthesis, Carbonic
Anhydrase Inhibitory Activity, Anticancer Activity and Molecular Modelling Studies. Eur. J.
Med. Chem. 2017, 139, 250–262. https://doi.org/10.1016/j.ejmech.2017.07.073.
(
(
20) Ejaz, S. A.; Saeed, A.; Siddique, M. N.; Nisa, Z. un; Khan, S.; Lecka, J.; Sévigny, J.; Iqbal, J.
Synthesis, Characterization and Biological Evaluation of Novel Chalcone Sulfonamide Hybrids as
Potent Intestinal Alkaline Phosphatase Inhibitors. Bioorg. Chem. 2017, 70, 229–236.
https://doi.org/10.1016/j.bioorg.2017.01.003.
21) Kobkeatthawin, T.; Chantrapromma, S.; Chidan Kumar, C. S.; Fun, H.-K. Synthesis,
Characterization, and Crystal Structure of Sulfonamide Chalcone: (E)-4-Methoxy-N-(4-(3-(3,4,5-
Trimethoxyphenyl)Acryloyl)Phenyl)-Benzenesulfonamide. Crystallogr. Reports 2015, 60 (7),
1
058–1064. https://doi.org/10.1134/S1063774515070135.
(
(
22) Custodio, J.; Michelini, L.; Castro, M.; Fonseca Vaz, W.; Neves, B. J.; Cravo, P.; Barreto, F.; de
Moraes, M. O.; Perez, C.; Napolitano, H. Structural Insights on a Novel Anticancer Sulfonamide
Chalcone. New J. Chem. 2018, 1–9. https://doi.org/10.1039/C7NJ03523C.
23) De Castro, M. R. C.; Aragão, Â. Q.; Da Silva, C. C.; Perez, C. N.; Queiroz, D. P. K.; Júnior, L. H.
K. Q.; Barreto, S.; De Moraes, M. O.; Martins, F. T. Conformational Variability in Sulfonamide
Chalcone Hybrids: Crystal Structure and Cytotoxicity. J. Braz. Chem. Soc. 2016, 27 (5), 884–898.
https://doi.org/10.5935/0103-5053.20150341.
(
24) de Castro, M. R. C.; Naves, R. F.; Bernardes, A.; da Silva, C. C.; Perez, C. N.; Moura, A. F.; de
Moraes, M. O.; Martins, F. T. Tandem Chalcone-Sulfonamide Hybridization, Cyclization and
Further Claisen–Schmidt Condensation: Tuning Molecular Diversity through Reaction Time and
2
5

Order and Catalyst. Arab. J. Chem. 2017. https://doi.org/10.1016/j.arabjc.2017.11.005.
(
25) Custodio, J. M. F.; Vaz, W. F.; de Castro, M. R. C.; Bernardes, A.; Naves, R. F.; Moura, A. F.; de
Moraes, M. O.; da Silva, C. C.; Martins, F. T.; Perez, C. N.; et al. Solvent-Driven Structural
Adaptation in a Novel Anticancer Sulfonamide Chalcone. J. Mol. Struct. 2019, 1175, 389–397.
https://doi.org/10.1016/j.molstruc.2018.07.059.
(
(
(
26) Gu, B.; Ji, W.; Patil, P. S.; Dharmaprakash, S. M. Ultrafast Optical Nonlinearities and Figures of
Merit in Acceptor-Substituted 3,4,5-Trimethoxy Chalcone Derivatives: Structure-Property
Relationships. J. Appl. Phys. 2008, 103 (10), 103511. https://doi.org/10.1063/1.2924419.
27) D’silva, E. D.; Podagatlapalli, G. K.; Rao, S. V.; Rao, D. N.; Dharmaprakash, S. M. New, High
Efficiency Nonlinear Optical Chalcone Co-Crystal and Structure–Property Relationship. Cryst.
Growth Des. 2011, 11 (12), 5362–5369. https://doi.org/10.1021/cg2009539.
28) Arshad, M. N.; Al-Dies, A.-A. M.; Asiri, A. M.; Khalid, M.; Birinji, A. S.; Al-Amry, K. A.; Braga,
A. A. C. Synthesis, Crystal Structures, Spectroscopic and Nonlinear Optical Properties of
Chalcone Derivatives: A Combined Experimental and Theoretical Study. J. Mol. Struct. 2017,
1
141, 142–156. https://doi.org/10.1016/j.molstruc.2017.03.090.
(
(
(
(
(
(
29) Kajamuhideen, M. S.; Sethuraman, K.; Ramamurthi, K.; Ramasamy, P. Growth and Physical
Characterization of Organic Nonlinear Optical Single Crystal: N,N -Diphenylguanidinium
′
Formate. Opt. Laser Technol. 2017, 91, 159–165. https://doi.org/10.1016/j.optlastec.2016.12.027.
30) Wyss, S.; Werner, I. A.; Schweizer, W. B.; Ametamey, S. M.; Milicevic Sephton, S. Preparation
and Structural Analysis of (±)-Threo-Ritalinic Acid. Acta Crystallogr. Sect. C Cryst. Struct.
Commun. 2013, 69 (11), 1225–1228. https://doi.org/10.1107/S010827011302595X.
31) Li, C.; Ji, Y.; Cao, Q.; Li, J.; Li, B. Concise and Facile Synthesis of ( R,R )-Dexmethylphenidate
Hydrochloride and Its Three Stereoisomers. Synth. Commun. 2017, 47 (14), 1301–1306.
https://doi.org/10.1080/00397911.2017.1293109.
32) Kim, J. H.; Ryu, W.; Shim, H.; Park, H. Development of New and Selective Trypanosoma Cruzi
Trans-Sialidase Inhibitors from Sulfonamide Chalcones and Their Derivatives. ChemBioChem
2
009, 701, 2475–2479. https://doi.org/10.1002/cbic.200900108.
33) d’Oliveira, G.; Moura, A.; de Moraes, M.; Perez, C.; Lião, L. Synthesis, Characterization and
Evaluation of in Vitro Antitumor Activities of Novel Chalcone-Quinolinone Hybrid Compounds.
J. Braz. Chem. Soc. 2018, 29 (11), 2308–2325. https://doi.org/10.21577/0103-5053.20180108.
34) Sheldrick, G. M. A Short History of SHELX. Acta Crystallogr. Sect. A Found. Crystallogr. 2008,
2
6

6
4 (1), 112–122. https://doi.org/10.1107/S0108767307043930.
(
(
(
35) Sheldrick, G. M. Crystal Structure Refinement with SHELXL. Acta Crystallogr. Sect. C Struct.
Chem. 2015, 71 (1), 3–8. https://doi.org/10.1107/S2053229614024218.
36) Spek, A. L. Single-Crystal Structure Validation with the Program PLATON. J. Appl. Crystallogr.
2
003, 36 (1), 7–13. https://doi.org/10.1107/S0021889802022112.
37) Nardelli, M. PARST95 – an Update to PARST: A System of Fortran Routines for Calculating
Molecular Structure Parameters from the Results of Crystal Structure Analyses. J. Appl.
Crystallogr. 1995, 28 (5), 659–659. https://doi.org/10.1107/S0021889895007138.
(
(
38) Farrugia, L. J. WinGX and ORTEP for Windows: An Update. J. Appl. Crystallogr. 2012, 45 (4),
8
49–854. https://doi.org/10.1107/S0021889812029111.
39) Macrae, C. F.; Edgington, P. R.; McCabe, P.; Pidcock, E.; Shields, G. P.; Taylor, R.; Towler, M.;
van de Streek, J. Mercury : Visualization and Analysis of Crystal Structures. J. Appl. Crystallogr.
006, 39 (3), 453–457. https://doi.org/10.1107/S002188980600731X.
ꢁ
2
(
40) Sheik-Bahae, M.; Said, A. A.; Wei, T.-H.; Hagan, D. J.; Stryland, E. W. Van. Sensitive
Measurement of Optical Nonlinearities Using a Single Beam. IEEE J. Quantum Electron. 1990, 26
(
4), 760–769. https://doi.org/10.1109/3.53394.
(
(
(
(
41) Göppert
‐ Mayer, M. Elementary Processes with Two Quantum Transitions. Ann. der Phisik 2009,
1
8 (7–8), 466–479. https://doi.org/10.1002/andp.200910358.
42) Clays, K.; Persoons, A. Hyper
‐ Rayleigh Scattering in Solution. Rev. Sci. Instrum. 1992, 63 (6),
3
285–3289. https://doi.org/10.1063/1.1142538.
43) Franzen, P. L.; Misoguti, L.; Zilio, S. C. Hyper-Rayleigh Scattering with Picosecond Pulse Trains.
Appl. Opt. 2008, 47 (10), 1443. https://doi.org/10.1364/AO.47.001443.
44) Costero, A. M.; Betancourt-Mendiola, M. L.; Gaviña, P.; Ochando, L. E.; Gil, S.; Chulvi, K.;
Peña-Cabrera, E. Structure and Conformational Studies of Aza-Crown 8-Amino-BODIPY
Derivatives: Influence of Steric Hindrance on Their Photophysical Properties. European J. Org.
Chem. 2017, 2017 (42), 6283–6290. https://doi.org/10.1002/ejoc.201701016.
(
45) da Costa, R.; Farias, F.; Maqueira, L.; Castanho Neto, C.; Carneiro, L.; Almeida, J.; Buarque, C.;
Aucélio, R.; Limberger, J. Synthesis, Photophysical and Electrochemical Properties of Novel D-
D and D- -A Triphenylamino-Chalcones and -Arylchalcones. J. Braz. Chem. Soc. 2019, 30 (1),
1–89. https://doi.org/10.21577/0103-5053.20180156.
π-
π
β
8
2
7

(
46) Fonseca, R. D.; Vivas, M. G.; Silva, D. L.; Eucat, G.; Bretonnière, Y.; Andraud, C.; De Boni, L.;
Mendonça, C. R. First-Order Hyperpolarizability of Triphenylamine Derivatives Containing
Cyanopyridine: Molecular Branching Effect. J. Phys. Chem. C 2018, 122 (3), 1770–1778.
https://doi.org/10.1021/acs.jpcc.7b05829.
(
(
47) Onsager, L. Electric Moments of Molecules in Liquids. J. Am. Chem. Soc. 1936, 58 (8), 1486–
1
493. https://doi.org/10.1021/ja01299a050.
48) Kamada, K.; Ohta, K.; Iwase, Y.; Kondo, K. Two-Photon Absorption Properties of Symmetric
Substituted Diacetylene: Drastic Enhancement of the Cross Section near the One-Photon
Absorption Peak. Chem. Phys. Lett. 2003, 372 (3–4), 386–393. https://doi.org/10.1016/S0009-
2
614(03)00413-5.
(
(
49) Neves, U. M.; De Boni, L.; Ye, Z.; Bu, X. R.; Mendonça, C. R. Two-Photon Absorption Spectra
of Salen Dye Complexes with Azo Dyes. Chem. Phys. Lett. 2007, 441 (4–6), 221–225.
https://doi.org/10.1016/j.cplett.2007.05.021.
50) Abegão, L. M. G.; Fonseca, R. D.; Santos, F. A.; Souza, G. B.; Barreiros, A. L. B. S.; Barreiros,
M. L.; Alencar, M. A. R. C.; Mendonça, C. R.; Silva, D. L.; De Boni, L.; et al. Second- and Third-
Order Nonlinear Optical Properties of Unsubstituted and Mono-Substituted Chalcones. Chem.
Phys. Lett. 2016, 648, 91–96. https://doi.org/10.1016/j.cplett.2016.02.009.
(
(
(
51) Lemes, S. R.; Júnior, L. A.; da Silva Manoel, D.; de Sousa, M. A. M.; Fonseca, R. D.; Lima, R. S.;
Noda-Perez, C.; de Melo Reis, P. R.; Cardoso, C. G.; de Paula Silveira-Lacerda, E.; et al. Optical
Properties and Antiangiogenic Activity of a Chalcone Derivate. Spectrochim. Acta Part A Mol.
Biomol. Spectrosc. 2018, 204, 685–695. https://doi.org/10.1016/j.saa.2018.06.099.
52) Custodio, J. M. F.; D’Oliveira, G. D. C.; Gotardo, F.; Cocca, L. H. Z.; De Boni, L.; Perez, C. N.;
Maia, L. J. Q.; Valverde, C.; Osório, F. A. P.; Napolitano, H. B. Chalcone as Potential Nonlinear
Optical Material: A Combined Theoretical, Structural, and Spectroscopic Study. J. Phys. Chem. C
2
019, 123 (10), 5931–5941. https://doi.org/10.1021/acs.jpcc.9b01063.
53) Santos, F. A.; Abegão, L. M. G.; Fonseca, R. D.; Alcântara, A. M.; Mendonça, C. R.; Valle, M. S.;
Alencar, M. A. R. C.; Kamada, K.; De Boni, L.; Rodrigues, J. J. Bromo-and Chloro-Derivatives of
Dibenzylideneacetone: Experimental and Theoretical Study of the First Molecular
Hyperpolarizability and Two-Photon Absorption. J. Photochem. Photobiol. A Chem. 2019, 369,
7
0–76. https://doi.org/10.1016/j.jphotochem.2018.10.012.
(
54) Oudar, J. L. Optical Nonlinearities of Conjugated Molecules. Stilbene Derivatives and Highly
2
8

Polar Aromatic Compounds. J. Chem. Phys. 1977, 67 (2), 446–457.
https://doi.org/10.1063/1.434888.
(
(
55) Campo, J.; Wenseleers, W.; Goovaerts, E.; Szablewski, M.; Cross, G. H. Accurate Determination
and Modeling of the Dispersion of the First Hyperpolarizability of an Efficient Zwitterionic
Nonlinear Optical Chromophore by Tunable Wavelength Hyper-Rayleigh Scattering. J. Phys.
Chem. C 2008, 112 (1), 287–296. https://doi.org/10.1021/jp0758824.
56) Orr, B. J.; Ward, J. F. Perturbation Theory of the Non-Linear Optical Polarization of an Isolated
System. Mol. Phys. 1971, 20 (3), 513–526. https://doi.org/10.1080/00268977100100481.
2
9