Benzenesulfonyl incorporated chalcones: Synthesis, structural and optical properties

Full text of DOI:10.1016/j.molstruc.2020.127845

Journal Pre-proof
Benzenesulfonyl incorporated chalcones: Synthesis, structural and optical properties
Jean M.F. Custodio, Fernando Gotardo, Wesley F. Vaz, Giulio D.C. D'Oliveira,
Leonardo Rodrigues de Almeida, Ruben D. Fonseca, Leandro H.Z. Cocca, Caridad
N. Perez, Allen G. Oliver, Leonardo de Boni, Hamilton B. Napolitano
PII:
S0022-2860(20)30169-1
DOI:
https://doi.org/10.1016/j.molstruc.2020.127845
MOLSTR 127845
Reference:
To appear in: Journal of Molecular Structure
Received Date: 12 December 2019
Revised Date: 30 January 2020
Accepted Date: 3 February 2020
Please cite this article as: J.M.F. Custodio, F. Gotardo, W.F. Vaz, G.D.C. D'Oliveira, L.R. de Almeida,
R.D. Fonseca, L.H.Z. Cocca, C.N. Perez, A.G. Oliver, L. de Boni, H.B. Napolitano, Benzenesulfonyl
incorporated chalcones: Synthesis, structural and optical properties, Journal of Molecular Structure
(2020), doi: https://doi.org/10.1016/j.molstruc.2020.127845.
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition
of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of
record. This version will undergo additional copyediting, typesetting and review before it is published
in its final form, but we are providing this version to give early visibility of the article. 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.
©
2020 Published by Elsevier B.V.

CRediT author statement
Jean M. F. Custodio: Conceptualization, Methodology, Supervision, Writing - Review & Editing
Fernando Gotardo: Formal analysis, Investigation, Writing - Original Draft.
Wesley F. Vaz: Writing - Original Draft
Giulio D. C. D’Oliveira: Writing - Original Draft.
Leonardo Rodrigues de Almeida: Writing - Original Draft
Ruben D. Fonseca: Writing - Original Draft
Leandro H. Z. Cocca: Writing - Original Draft
Caridad N. Perez: Supervision, Writing - Review & Editing, Resources
Allen G. Oliver: Supervision, Writing - Review & Editing, Resources
Leonardo de Boni: Writing - Review & Editing, Resources
Hamilton B. Napolitano: Supervision, Writing - Review & Editing

Benzenesulfonyl Incorporated chalcones: Synthesis, Structural and
Optical Properties
Authors
a
b
c
a
Jean M. F. Custodio *, Fernando Gotardo , Wesley F. Vaz , Giulio D. C. D’Oliveira , Leonardo
b
bd
b
a
Rodrigues de Almeida , Ruben D. Fonseca , Leandro H. Z. Cocca , Caridad N. Perez , Allen G.
e
b
c
Oliver , Leonardo de Boni and Hamilton B. 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
e
Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana, 46556, USA
Correspondence email: jeanmfcustodio@gmail.com; hbnapolitano@gmail.com
Synopsis A set of new sulfonamide chalcones hybrids is presented. Their structural and optical
properties are investigated
Abstract Although the optical properties and applicability of chalcones as potential nonlinear optics
(
NLO) materials is well known, hybrids having both chalcone and sulfonamide portions are relatively
scarce yet. In this sense, we are seeking to show if combining both into a double functionalized
compound will still have similar or better NLO responses. For this, we have synthetized three
sulfonamide-chalcone analogues by changing the substituent bonded to the sulfonamide ring (I = ethoxy;
II = Cl and III = Br). These compounds were characterized by spectroscopic methods (NMR, IR and
HRMS) and thermal methods (HSM and DSC/TGA). Their crystal structures were determined by Single
Crystal X-ray Diffraction (SCXRD) and their molecular structures were compared. Crystallographic
results showed that one compound crystallizes in a triclinic system whereas the others crystallize in a
monoclinic crystal system. Moreover, their crystal packing is dominated by C–H⋯O interactions. In
addition to this study and to first characterize these compounds, linear and nonlinear optical (NLO)
properties were performed in all three compounds dissolved in dimethyl sulfoxide. One-photon and two-
photon absorption (2PA) spectra and incoherent second harmonic generation were obtained by employing
different spectroscopic techniques. The interesting results observed in the linear and NLO measurements
showed that different groups bounded to the same main backbone did not significantly modify their

optical properties, although they strongly affect their crystal structures.
excited state is allowed by both 1PA and 2PA, which indicates asymmetry in the charge distribution along
the -conjugated molecule structure. NLO properties of compounds I-III agree with other chalcones
σ2PA spectra reveal that the first
π
previously studied, which indicates that adding the benzenossulfonyl group does not influence these
properties. Considering the similar experimental values for different substituents, this results motivate
further investigation on substituent-based optical properties for other sulfonamide-chalcone hybrids.
Keywords: Sulfonamide chalcone; nonlinear optical properties; hybrid compounds
1
. Introduction
Chalcones and their derivatives have been extensively studied because of their wide range of
applicability. The presence of the reactive keto-ethylenic group and two aryl rings linked by an enone
group is responsible for most of the biological properties observed for these compounds (Tajuddeen et al.,
2
018; Singh et al., 2014). Many biological potentials, such as anticancer (Kamal et al., 2012; Custodio et
al., 2018), antituberculosis (Lin et al., 2002), antileishmanial (Zhai et al., 1999) and therapeutical
Mahapatra & Bharti, 2016) have been attributed to chalcones, and their use as potential optical devices
has also been studied. Chalcones have delocalized electronic charge distribution and -orbitals; this leads
to a high electron density mobility making them ideal candidates for nonlinear optical (NLO) materials
Shetty et al., 2018).
(
π
(
Not only is the chalcones backbone, but also the substitution pattern around their aromatic rings is
responsible for observed NLO properties. Abegão and co-workers reported an increase in the 2-photon
absorption (2PA) and hyper-Rayleigh scattering (HRS) of two chalcones when an aromatic hydrogen
atom was replaced by the radical methoxyl (Abegão et al., 2016). Also, chalcones derivatives with
3
different groups (Br and NO ) presented different third order susceptibility
χ
and second order
2
hyperpolarizabilityγh when measured using picosecond laser pulses by Z-scan technique (D’silva et al.,
012). Similar, structural changes in chalcone derivatives can modify different optical properties such as
2
refractive index, absorption magnitude and spectral position , as well the optical energy gap (Makhlouf et
al., 2018). These examples indicate that even with same backbone, structurally modified chalcones can
exhibit variable physical properties. Furthermore, some examples of optically active sulfonamide
compounds are known. Polymeric materials containing sulfonamide-substituted azobenzene
chromophores were investigated and found to have good NLO response (Ra
źna et al., 1999); benzene
sulfonamide derivatives have also shown good NLO activity (Sarojini et al., 2013). Beyond experimental
2

results, theoretical calculations determined for this class of compounds have also provided excellent
simulations (Govindasamy & Gunasekaran, 2015).
Although the optical properties and applicability of chalcones as potential NLO materials is well known,
double functionalized compounds having both chalcone and sulfonamide portions are relatively scarce.
Having in mind these results for chalcones and sulfonamides separately, we are seeking to show if
combining both into a double functionalized compound will still have similar or better NLO responses.
Herein, we present a new set of benzenesulfonyl incorporated chalcones with the same π-conjugated
backbone bearing distinct charge groups. The synthesized molecules are sulfonamide chalcones, which
are (E)-N-(2-(3-(4-ethoxyphenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (I), (E)-3-(4-
chlorophenyl)-1-(2-(phenylsulfonylamine) phenyl)prop-2-en-1-one (II) and (E)-3-(4-bromophenyl)-1-(2-
(
phenylsulfonylamine)phenyl)prop-2-en-1-one (III). In addition to their structural study, these
13
1
compounds were full characterized using a variety of spectroscopic techniques, such as C and H
Nuclear Magnetic Resonance (NMR), Infrared (IR), High Resolution Mass Spectroscopy (HRMS),
Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA) and Hot Stage microscopy
(
HSM). We determined the linear and nonlinear optical properties of all compounds dissolved in dimethyl
sulfoxide. One- photon (1PA) and two-photon absorptions (2PA), as well as incoherent molecular second
harmonic generation, were measured to elucidate the dependence of these properties with the molecular
structure.
2
. Experimental
2
.1. Materials and Apparatus
1
13
H NMR and C NMR spectra were recorded by a 400 MHz Bruker Avance III 11.75 T NMR
spectrometer. Infrared studies were performed with a PerkinElmer Frontier Dual Range FTIR/IR
Spectrometer, measured in Attenuated Total Reflectance mode. Mass spectrometric analyses were
performed using a MicroTOF-Q® III spectrometer equipped with a commercial ESI ion source (Bruker
1
Daltonics, Bremen, Germany). 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.
Fluorescence and linear absorption over the UV-Vis-NIR region were performed in solution, respectively,
by using HITACHI F7000 fluorimeter and SHIMADZU UV-1800 spectrometer. The solutions were
-
prepared with the samples dissolved in dimethyl sulphoxide (DMSO) in a concentration of about 10
5
mol/L. For both measurements, a fused silica cuvette with optical path length of 10 mm was used as
solution confinement tool.
3

2
2
.2. Synthesis and Crystallization
.2.1. General procedures
2
2
’N-phenylsulfonylacetophenone (a), was synthesized by reaction between benzenesulfonyl chloride and
-aminoacetophenone in dichloromethane (Scheme 1), based on a literature preparation previously
described(de Castro et al., 2017). Compounds I-III were synthesized using the methodology reported by
Castro(De Castro et al., 2016) via base catalysis (Scheme 2).
2
.2.2. Synthesis of the intermediate 1-(2-(phenylsulfonylamino)phenyl) ethanone (a)
Benzenesulfonyl chloride (70.65 g, 0.40 mol), 2-aminoacetophenone (67.58 g, 0.50 mol) and
triethylamine (50.55 g, 0.50 mol) were dissolved in 500 mL of dichloromethane and kept in the
refrigerator for 37 h, following Scheme 1. The solution was filtered and the resulting crystals rinsed with
methanol.
O
O
O
S
TEA; DCM
ºC; 37 h
Cl
+
0
NH2
O
NH
a
SO Ph
2
Scheme 1 General conditions for the synthesis of 2’N-phenylsulfonylacetophenone (a)
2
.2.3. Synthesis of compounds I, II and III
-1
Precursor a, the substituted benzaldehyde and catalytic amount of potassium hydroxide (141 mmol.L )
reacted at room temperature. Then, water (0.08 L) and hydrochloric acid were added, following Scheme
2
. The product was extracted with dichloromethane and the crystals were obtained by direct evaporation
of this solution. The benzaldehyde, time of reaction and amount of each reactant are presented in Table
S1.
4

Scheme 2 General conditions for the synthesis of compounds I, II and III.
2
.3. Physico-chemical Caracterization
1
1
-(2-(phenylsulfonylamino)phenyl) ethanone (a): Yield, 55.1 g (50.1%) of a white crystalline solid. H
2.56 (s, 3H), 7.08 (ddd, J 7.98 Hz, 7.33 Hz, 1.18 Hz, 1H), 7.42 – 7.46 (m, 2H), 7.46
dddd, J 8.44 Hz, 7.34 Hz, 1.56 Hz, 0.41 Hz, 1H), 7.51 – 7.54 (m, 1H), 7.70 (ddd, J 8.40 Hz, 1.15 Hz,
NMR (CDCl3)
δ
δ
(
13
0
.45 Hz, 1H), 7.80 (ddd, J 8.01 Hz, 1.59 Hz, 0.46 Hz, 1H), 7.84 – 7.87 (m, 2H), 11.50 (s, 1H); C NMR
(
CDCl
3
)
δ
28.17, 119.25, 122.41, 122.77, 127.24, 129.05, 131.91, 133.01, 134.97, 139.48, 139.92,
+
2
2
02.43; HRMS (High-Resolution Mass Spectrometry) calculated for [C H NO S + H] 276.0694, found
14
12
3
76.0725.
(
E)-N-(2-(3-(4-ethoxyphenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (I): Yellow
o
crystalline solid, yield 76.1%, purity of 98.1%, mp 137 – 140 C. 1H NMR (CDCl3)
δ
1.45 (t, J 7.00 Hz,
3
7
8
7
1
1
H),
.20 (d, J 15.50 Hz, 1H),
.38 Hz, 1H), 7.53 – 7.56 (m, 2H),
.80 – 7.84 (m, 3H), 11.22 (s, 1H) (Fig S1 and Table S2); 13C NMR (CDCl3)
δ
4.09 (q, J 7.00 Hz, 2H),
7.35 – 7.39 (m, 2H),
7.65 (d, J 15.50 Hz, 1H),
δ
6.91 – 6.94 (m, 2H),
7.40 – 7.44 (m, 1H),
7.75 (dd, J 1.03 Hz, 8.33 Hz, 1H),
14.7, 63.8, 115.0,
δ
7.13 (ddd, J 1.25 Hz, 7.38 Hz, 7.88 Hz,1H),
δ
δ
δ
δ
7.47 (ddd, J 1.45 Hz, 7.40 Hz,
δ
δ
δ
δ
δ
δ
19.5, 120.9, 123.2, 125.3, 127.0, 127.3, 129.0, 130.4, 130.5, 132.8, 134.0, 139.5, 139.7, 146.1, 161.6,
92.7 (Fig S2 and Table S3); IR 1637 (m), 1497 (m), 1329 (s), 927 (m), 761 (s); HRMS calculated for
+
[
C H NO S + Na] 430.1089, found 430.1103.
23
21
4
(
E)-3-(4-chlorophenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (II): Yellow crystalline
o
1
solid, yield 70.9%, purity of 98.2%, mp 150 – 155 C. H NMR (CDCl )
δ
7.14 (ddd, J 1.16 Hz, 7.34 Hz,
7.43 – 7.46 (m, 1H), 7.50 (ddd, J 1.55
7.63 (d, J 15.55 Hz, 1H), 7.75 (dd, J 1.08 Hz, 8.33
11.18 (s, 1H) (Fig S3 and Table S2); C NMR (CDCl 120.7, 122.5,
23.2, 124.6, 127.3, 129.0, 129.4, 129.7, 130.6, 132.9, 132.9, 134.5, 137.0, 139.5, 140.0, 144.5, 192.5
3
7
.94 Hz, 1H),
Hz, 7.40 Hz, 8.40 Hz, 1H),
Hz, 1H), 7.82 – 7.85 (m, 3H),
δ
7.33 (d, J 15.55 Hz, 1H),
δ
7.37 – 7.42 (m, 4H),
δ
δ
δ
7.52 – 7.55 (m, 2H),
δ
δ
13
δ
δ
3
) δ
1
(
[
Fig S4 and Table S3); IR 1641 (m), 1492 (m), 1329 (m), 928 (m), 756 (m); HRMS calculated for
+
C H ClNO S + H] 398.0618, found 398.0462.
21
16
3
(
E)-3-(4-bromophenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (III): Yellow crystalline
o
1
solid, yield 52.0%, purity of 97.1%, mp 157 – 159 C. H NMR (CDCl )
δ
7.14 (ddd, J 1.15 Hz, 7.35 Hz,
7.42 – 7.47 (m, 3H), 7.49 (ddd, J 1.54
7.61 (d, J 15.55 Hz, 1H), 7.75 (dd, J 0.80 Hz, 8.35
3
7
.90 Hz, 1H),
δ
7.34 (d, J 15.55 Hz, 1H),
δ
7.37 – 7.40 (m, 2H),
δ
δ
Hz, 7.34 Hz, 8.41 Hz, 1H),
δ
7.55 – 7.58 (m, 2H),
δ
δ
5

13
Hz, 1H),
3
δ 7.81 – 7.84 (m, 3H), δ 11.17 (s, 1H) (Fig S5 and Table S2); C NMR (CDCl ) δ 120.7, 122.6,
1
23.2, 124.6, 125.4, 127.3, 129.0, 129.9, 130.6, 132.4, 132.9, 133.3, 134.5, 139.4, 140.0, 144.5, 192.5
(
[
Fig S6 and Table S3); IR 1640 (m), 1489 (m), 1331 (m), 924 (m), 751 (s); HRMS calculated for
+
C H BrNO S + H] 442.0113, found 442.0004.
21
16
3
2
.4. Refinement
Single crystals of I were selected and mounted in an Agilent SuperNova diffractometer, whereas for
single crystals of II and III a Bruker APEX II CCD diffractometer was used. Data were recorded with
graphite-monochromated MoKa radiation (λ = 0.71073 Å) at room temperature. The data collection, cell
refinements and data reduction were performed using CrysAlis PRO (Rigaku, 2015) for I, and SAINT
software (Bruker, 2009) for II and III. The structures were solved with ShelXS (Sheldrick, 2008) by
direct methods and refined with ShelXL (Sheldrick, 2015) by least squares minimization. As
implemented in Olex2 (Dolomanov et al., 2009) all the hydrogen atoms were placed in calculated
positions and refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C)]
according to the riding model. The structural analysis was performed using Mercury (Macrae et al.,
2
008). The possible interactions and hydrogen bonds were checked by using PARST (Nardelli, 1995) and
PLATON (Spek, 2009). The crystallographic information files of I, II and III were deposited in the
Cambridge Structural Data Base (CCDC) (Allen, 2002; Groom & Allen, 2014) under the codes 1949073,
1
949070, 1949072, respectively. Copies of the data can be obtained, free of charge, via
www.ccdc.cam.ac.uk.
2
2
.5. Nonlinear optical measurements
.5.1. Two-Photon Absorption
Z-Scan technique(Sheik-Bahae et al., 1990), using a tunable 120 femtosecond coherent light source, was
employed to determine two-photon absorption (2PA) cross section spectra. This technique consists of
measuring the transmittance as function of the position of the sample along the z-direction, focusing the
laser beam by a convergent lens. The transmittance is normalized by taking the ratio of the transmittance
at z-positions over the transmittance far from the focus, thus the normalized transmittance (ꢀ(ꢁ)) is
calculated by:
∞
1
ꢉꢊꢋ
ꢀ
(ꢁ) =
ꢅ ꢆꢇ[1 + ꢃ (ꢁ, 0)ꢈ ]ꢌꢍꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎ(1)
ꢄ
√
ꢂꢃ
ꢄ
(ꢁ, 0) ꢉ∞
6

ꢖꢋ
ꢋ
ꢉꢙ
ꢘ
in which, z is the position of the sample with respect to the focus (z = 0), ꢃꢄ = ꢏ ꢓ ꢔ ꢕ1 +
.
ꢓꢄ is
ꢐꢑꢒ ꢄ
ꢖ
ꢗ
the intensity of the laser pulse, ꢁꢄ is the Rayleigh length, L is the optical path length, and ꢏꢐꢑꢒ is the
nonlinear absorption coefficient. The 2PA cross section (ꢚꢐꢑꢒ) can be calculated by:
ℏꢛ
ꢚꢐꢑꢒ
is the frequency of the light,
=
ꢏꢐꢑꢒꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎ(2)
ꢜ
3
in which,
ꢛ
ℏ
is Planck constant, and N is the density of molecules per cm .
The unit used for the 2PA cross section is GM (Göppert-Mayer; 1ꢎꢝꢞ = 1 × 10ꢉꢟꢄꢎꢠꢡ ⋅ ꢣ ⋅ ꢤℎꢥꢍꢥꢇꢉꢙ)
ꢢ
(
Göppert‐ Mayer, 2009).
To perform this experiment, the experimental setup includes a tunable optical amplifier (TOPAS), a
Ti:Sapphire (CPA 2001 from Clark-MXR Inc.) laser, silicon photodetectors and locking amplifiers. The
Ti:Sapphire emits at 775 nm wavelength with a pulsewidth of 150 fs in a repetition rate of 1 kHz. It is
used to pump TOPAS, which tunes the wavelength of the light in a range from 470 nm to 800 nm with
pulsewidths of about 120 fs. A 15 cm convergent lens focuses this tuned light in the region that the
sample is translated. Two Silicon photodetectors are used to collect signals from the Z-Scan
measurements; one uses to measure the transmitted light for each position, z, of the sample, and other
used as reference of laser intensity fluctuations. Locking amplifiers amplify and average the signals from
the two photodetectors in order to increase the signal:noise ratio.
2
.5.2. Incoherent second harmonic generation (First order hyperpolarizability)
The first hyperpolarizability (ꢦ) of the chalcone derivatives was determined by the Hyper-Rayleigh
Scattering technique (HRS) (Clays & Persoons, 1992; Franzen et al., 2008) in which a Nd:YAG Q-
Switched and mode-locked laser that delivers a train of pulses at 1064 nm wavelength was employed.
This pulse train contains of about 30 pulses of 100 ps each, separated by 13.2 ns from each other (Franzen
et al., 2008). Laser was set to operate at 100 Hz of repetition rate. Pulses are focalized at the sample that
scatters the second harmonic (532 nm) of the incident light and then is collected by a photomultiplier
positioned at an angle of 90° with the incident light. In addition to that, an optical filter centered at 532
nm with 10 nm of bandwidth is positioned in front of the photomultiplier to block extra light that could
interfere with the desired signal. The intensity of the scattered light, ꢓ(2ꢛ), and the incident laser light,
ꢓ(ꢛ), are related by:
ꢩ
ꢐ ꢐ
ꢓ(2ꢛ) = ꢧ ꢝꢜ ꢦ ꢓ (ꢛ)ꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎ(3)
ꢨ
ꢨ
ꢨꢪꢙ
7

in which, G is an instrumental constant determined during experimental setup based on a well-known
standard sample, and ꢜꢨ is the molecular concentration. The calibration sample chosen was para-
Nitroaniline (pNA) dissolved in DMSO that presents a ꢦ(1064ꢇꢡ) = 26.2 × 10ꢉꢫꢄꢎꢠꢡ /ꢈꢣꢬ (Franzen
et al., 2008). Acquisition of data for several concentration of a chalcone derivative gives a linear relation
ꢟ
between ꢓ(2ꢛ) and ꢜꢨ, in which an angular coefficient (ꢏꢭꢮꢯꢰꢭꢱꢲꢳ
of the pNa (ꢏꢴꢵꢒ can be found by repeating this procedure for different pNa molecular concentrations.
The first hyperpolarizability of the chalcone (ꢦꢭꢮꢯꢰꢭꢱꢲꢳ is related to these angular coefficients by:
) is determined. The angular coefficient
)
)
ꢏꢭꢮꢯꢰꢭꢱꢲꢳ
ꢏꢴꢵꢒ
ꢐ
ꢦꢭꢮꢯꢰꢭꢱꢲꢳ
=
ꢦ
ꢎꢎꢎꢎꢎꢎꢎꢎꢎ(4)
ꢶ
ꢴꢵꢯ
in which, ꢏꢭꢮꢯꢰꢭꢱꢲꢳ = ꢝꢦꢐ
and ꢏꢴꢵꢒ = ꢝꢦꢐ
.
ꢭꢮꢯꢰꢭꢱꢲꢳ
ꢴꢵꢒ
2
.6. Thermal characterization
Thermogravimetric analyses (TGA) were carried out on a Shimadzu TGA-60 thermobalance, using
approximately 5.0 mg of sample placed on aluminium pans and heated from room temperature up to 500
-1
-1
°
C, at 10 °C.min , under nitrogen flow (50 mL.min ). Differential scanning calorimetric (DSC)
measurements were performed on a Shimadzu DSC-60 instrument. Samples (2.5 ± 0.5 mg) were placed at
-1
aluminium pans and heated from room temperature up to 400 °C, at 10 °C min , under nitrogen flow (50
-1
mL.min ). All data were processed using the Shimadzu TA-60 thermal data analysis software (version
2
.2). Hot-stage microscopy (HSM) was performed on a Leica DM2500P microscope connected to an
Linkam T95-PE hot-stage apparatus. Data were visualized with the Linksys 32 software for hot stage
control. The crystals of compounds I, II and III were placed on a 13 mm glass coverslip, placed on a 22
mm diameter pure silver heating block inside of the stage. The samples were heated at a ramp rate of 10
-1
°
C.min up to a temperature required to melting of all material.
3
3
. Results and discussion
.1. Solid state characterization
The synthesized compounds have a common chalcone backbone, composed of two aromatic rings
connected through a three-carbon bridge (with one -unsaturation) having a keto carbonyl group, and
an o-benzenesulfonamide group attached to ring A. Compounds I-III differ each other by the substituent
at p-position of ring C (I = OEt, II = Cl, and III = Br). Compound I crystallizes in the space group P2 /c
α,β
1
8

whereas II and III, each with two independent molecules (
α
and
ꢷ
1. Experimental details are shown in Table 1 and their ORTEP diagrams are presented in
ω) in asymmetric unit, crystallize in
space group P
Fig. 1.
Table 1 Crystal structure and refinement data of I, II and III
(
I)
(II)
(III)
Table 2
Crystal data
Chemical
formula
C H NO S
C H ClNO S
2(C H BrNO S)
2
3
21
4
21 16
3
21 16
3
M
r
407.47
397.86
884.63
Crystal system, Monoclinic, P2
1
/c
Triclinic, P1
Triclinic, P1
space group
Temperature
K)
294
296
296
(
a, b, c (Å)
8.8384 (5), 26.6514 (16), 8.4130 (4), 9.8066 (5), 13.1211
.7741 (4) (7)
8.5051 (9), 12.1557 (15), 19.520
(2)
8
α, β, γ (°)
90, 90.963 (5), 90
73.231 (2), 85.049 (2), 69.892 (2) 101.955 (4), 99.056 (4), 92.558 (4)
3
V (Å )
2066.5 (2)
4
973.22 (9)
1943.5 (4)
Z
2
2
Radiation type Mo Kα
Mo Kα
Mo Kα
−
1
µ (mm )
0.19
× ×
0.32
2.24
Crystal size
0.48 × 0.40 × 0.28
0.42 × 0.30 × 0.29
(
mm)
Data collection
Diffractometer SuperNova, Dual, Cu at
zero, AtlasS2
Bruker APEX-II CCD
Bruker APEX-II CCD
Absorption
correction
Multi-scan
Multi-scan
Multi-scan
CrysAlis PRO 1.171.38.46 SADABS2014/5 (Bruker,2014/5) SADABS2014/5 (Bruker,2014) was
9

(
Rigaku Oxford
was used for absorption
correction. wR2(int) was 0.1499 wR2(int) was 0.1590 before and
before and 0.0735 after 0.0451 after correction. The Ratio
used for absorption correction.
Diffraction, 2015)
Empirical absorption
correction using spherical correction. The Ratio of minimum of minimum to maximum
harmonics, implemented in to maximum transmission is transmission is 0.7271. The λ/2
SCALE3 ABSPACK
scaling algorithm.
0.8342. The λ/2 correction factor correction factor is 0.00150.
is 0.00150.
Tmin, Tmax
0.686, 1.000
0.622, 0.745
0.542, 0.745
No. of
71464, 5570, 4391
37156, 4007, 2917
68586, 7942, 5855
measured,
independent and
observed [I >
2
σ(I)]
reflections
Rint
0.039
0.694
0.050
0.626
0.038
0.625
(
(
sin θ/λ)max
−
1
Å )
Refinement
2
2
R[F > 2σ(F )], 0.054, 0.131, 1.11
0.044, 0.121, 1.02
0.040, 0.102, 1.03
2
wR(F ), S
No. of
5570
267
4007
248
0
7942
495
36
reflections
No. of
parameters
No. of restraints 0
H-atom
H atoms treated by a
H atoms treated by a mixture of H atoms treated by a mixture of
treatment
mixture of independent and independent and constrained
independent and constrained
refinement
constrained refinement
refinement
0.30, −0.26
ꢀρmax, ꢀρmin (e 0.28, −0.29
0.73, −0.75
−
3
Å )
1
0

Computer programs: CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015), SHELXS (Sheldrick, 2008), SHELXL
Sheldrick, 2015), Olex2 (Dolomanov et al., 2009).
(
Figure 1 The ORTEP diagram of ellipsoids at 50% probability level with the atomic numbering scheme
for the asymmetric unit of I (a), II (b) and III (c). The atomic numbering labels for ω molecule (c) is
equal to α molecule but differ by asterisk (*) symbol. Hydrogen atoms are represented as spheres with
arbitrary radii and its labels attributed followed the corresponding attached atom
Molecular planarity is an important parameter and should be considered when studying the physical
properties of a compound. Nevertheless, higher the number of donor-receptor interactions in a molecule,
better will be the electron transfer and nonlinearity. Thus, more planar is a molecule with conjugated π-
electrons bridge, more these characteristic interactions will be expected to occur (Kumar et al., 2011;
Menezes et al., 2015). I and II could be considered planar molecules, observing that the angle between
the planes of rings A and B in these molecules are 4.56° and 7.72° respectively. Meanwhile in III, the α
molecule also could be considered planar, with angle equal to 4.24°. However, in ω, this planarity is
decreased, and the rings form an angle of 16.37°. An overlay of molecules I, II, III-α and III-ω is
depicted in Fig. 2. There are four previously reported structures of o-sulfonamide-chalcones (de Castro et
1
1

al., 2017). One of them (ref-code: QERNEJ, here mentioned as NAB) has only substituents at para
position of the ring B. Structural parameters of NAB and I, II, and III differ each other by the angle
formed between rings A and B, as well as the torsion angle N1-S1-C16-C17.
Figure 2 Conformational differences between the compounds I [cyan], II [blue], IIIα [white] and IIIω
[
black]
The crystal packings of I, II and III, shown in Fig. 3, are dominated by C–H⋯O interactions, as shown in
Table 2, leading to a dimer-stabilized arrangement and bifurcated intermolecular interactions. Such
arrangements are also present in similar compounds (de Castro et al., 2017; Castro et al., 2013; Seo et al.,
2
010; Custodio, Vaz et al., 2019; De Castro et al., 2016; Custodio et al., 2018). The crystal packing of I
(
Fig 4a) is stabilized by three C–H⋯O interactions involving the atom O2 and chains along the c-axis.
Similar to NAB, the aromatic ring C is almost perpendicular (74.03°) to the plane formed by the chalcone
backbone along this chain. In contrast, the C–H⋯O interactions in the extended structure of II (Fig. 4b) is
ꢐ
composed of dimers with ꢸ (14) motif, involving SO group and the ring A, through C8–H8⋯O2 and
ꢐ
2
C12–H12⋯O1 interactions (Fig. 4c). Thus, the crystal packing in II is stabilized by a chain parallel to the
a-axis. In addition, the dimer has an inversion center which orients the C rings in opposite directions.
Table 3 Non-classical hydrogen-bond geometry (Å, º) for I, II and III.
D—H···A
D—H
H···A
D···A
D—H···A
I
i
i
C8—H8···O2
C5—H5···O2
0.93
0.93
0.93
2.47
2.56
2.54
3.355 (2)
3.399 (2)
3.388 (2)
159
150
151
i
C11—H11···O2
II
1
2

ii
C8—H8···O2
0.93
0.93
0.93
2.49
2.53
2.65
3.308 (3)
3.360 (3)
3.418 (3)
148
148
141
ii
C12—H12···O1
iii
C3—H3···O3
III
ii
C8—H8···O2
0.93
0.93
0.93
0.93
0.93
2.41
2.49
2.59
2.49
2.61
3.283 (3)
3.262 (4)
3.442 (4)
3.321 (3)
3.422 (4)
156
140
153
148
147
ii
ii
C11—H11···O2
C12—H12···O1
ii
C8*—H8*···O2*
C14*—H14*···O1*
ii
Symmetry code: (i) x, y, z+1; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+2.
Figure 3 Molecular packing of I (a), II (b) and III (c).
On the other hand, in the packing of III, there are, in α molecule, two C–H⋯O contacts leading to
propagation parallel to the a-axis (Fig 4d). The first involves SO group and H atoms of ring B (C11–
2
ꢙ
H11⋯O2) and vinyl group (C8–H8⋯O2) forming a ꢸ (7) motif, whereas C12–H12⋯O1 interaction
ꢐ
involves carbonyl group and H atom of ring B. About ω molecule, C8*–H8*⋯O2* and C14*–
ꢐ
H14*⋯O1* interactions form a ꢸ (14) motif parallel to a-axis (Fig. 4e).
ꢐ
1
3

Figure 4 C–H⋯O interactions present in the crystal packing of I, II and III.
3
.2. One-, two-photon absorption spectra and molecular second harmonic generation.
Fluorescence emission signals for all three sulfonamide chalcones dissolved in DMSO solvent were not
observed by exciting the sample at different wavelengths in the absorption bands. This indicates that the
decay from the first singlet excited state to the ground state take place in a nonradioactive relaxation
process when molecules are in DMSO solutions. Figure 5 shows molar absorptivities (dashed blue lines)
of the three chalcones derivatives, in which the lower electronic transition is located around 355 nm for
molecule I, and it is blue shifted of about 30 nm for molecules II and III, now located at 320 nm.
1
4

Figure 5 Molar absorptivity (ε) (dashed blue lines) and two-photon absorption cross section (open red
circles) spectra of chalcones I (a), II (b) and III (c) dissolved in DMSO solvent. The black lines are the
adjustments obtained with Sum-Over-States model. Molar absorptivity was measured using a
-4
-1
concentration of 10 mol.L at room temperature.
-1
-1
Maximum values of the molar absorptivity were found to be of about 23000 mol L cm for molecule I
(
see Fig. 5(a)), and for molecules II and III (see Fig.5(b) and (c) respectively of about 25000 and 28000
-1
-1
mol L cm respectively. For wavelengths longer than 500 nm, the compounds do not present any
additional absorption bands at the UV-VIS-NIR region. Furthermore, Fig. 5 also depicts 2PA spectra
(
open red circles) along with their Sum Over States approach model adjustment (continuous black line).
Each open red circle is the two-photon absorption cross section value obtained by adjusting the Z-Scan
measurements with Eq. (1). As can be seen, the lowest energetic 2PA band matches with the lowest
energetic one photon absorption, which indicates that the electronic state is allowed by one- and two-
photon absorption spectrum. The charge asymmetry in the sulfonamide chalcones allows that the
transition selection rules for the dipole electric moment, in this type of conjugated molecules, may be
relaxed, permitting an electronic state to absorbs one or two-photons.
The 1PA absorption is red-shifted for molecule I with respected to molecules II and III, this effect may
be assigned by the higher molecular planarity combined with the electronegativity of the ethoxy group
when compared to bromine and chlorine atoms. However, changes between chlorine and bromine atoms,
in the para position of the sulfonamide chalcones, do not modify significantly both molar absorption
magnitude and, as well, the energy value of the lowest energetic band. As mentioned before, a small red-
shift is observed only for chalcone with ethoxy group, indicating a small reduction in the energy of the
lowest electronic state. Similar characteristics are also observed in the 2PA spectrum: the highest 2PA
cross section of about 26 GM at 720 nm (see Fig. 5(a)) was observed for I and it is red-shifted, as well,
when compared to II and III, following the same behavior of 1PA absorption.
1
5

Compounds II and III, showed small values of about 14 GM and 17 GM respectively (Fig. 5(b) and (c)).
These two molecules present a two-photon allowed-band centered approximately at 560 nm with
maximum values of 18 GM and 14 GM respectively. This band does not have a similar in the 1PA at 280
nm, which means that the electronic state located at 280 nm is allowed by 2PA. This band was not
measured for compound I due to the red-shift of the lowest energetic state. Also, all 2PA spectrum
presented a monotonically increase of the 2PA cross sections for wavelengths shorter than 510 nm, which
is caused by the resonance enhancement effect. This effect occurs when the photon energy is close in
energy to the first excited transition state, increasing the 2PA probability to occur.
Both, one- and two-photon absorption results indicate that the electronic states of the chalcones were not
affected by replacing chlorine atom with bromine. Only the ethoxy group showed a slight difference
between the three molecules. This can be explained by the distinct electronegativities of the different
substituents, which should be responsible by different charge distribution in the molecules. As can be
seen in the structures of I, II and III, the main molecular skeleton is identical for all, which may
indicates, a priori, the same conjugation length. However, the reduction in planarity can also decrease the
magnitude of the one- and two-photon absorption cross sections as well blue shift the optical transitions.
As mention in section 3.1 (Solid state characterization), molecule III shows to have the lower degree of
planarity comparing to the other two molecules, when III is in ω conformation. However, the optical
properties show to be close in values between all three samples, which indicates that in solution, molecule
III majority conformation may be α. In summary, as the main structures look essentially the same, it is
expected that optical properties should also be similar in magnitude.
The transition dipole moment related to the lowest electronic state, which gives the strength of the
transition was evaluated considering the experimental molar absorptivity. As all sulfonamide chalcones
studied here present one absorption band at approximately 350 nm (lowest energy band), the transition
dipole moment related to the transition from the ground state to the first singlet excited state, ꢹ , is
ꢄꢙ
determined by:
ꢫ
3
⋅ 10 ꢆꢇ(10)ℏꢠ ꢇ
ꢐ
μ
=
∫ ꢺ(ꢛ)ꢌꢛꢎꢎꢎꢎꢎꢎ(5)
ꢄꢙ
ꢫ
ꢔꢐ
(
2ꢂ) ꢜ ꢛ
ꢒ
ꢄꢙ
in which, ꢠ is the speed of light, ℏ is Planck’s constant, ꢜ is Avogadro’s number, ꢛ is the transition
ꢒ
ꢄꢙ
ꢫꢲꢋ
ꢐ
frequency of the first excited state, ꢇ is the refraction index of solvent (for DMSO, ꢇ = 1,42), ꢔ =
ꢋ
ꢐꢲ ꢻꢙ
is the Onsager local field factor (Onsager, 1936), and ꢺ is the molar absorptivity. Calculated values for
ꢹꢄꢙ are depicted in Table 3 together with other parameters determined by Sum-Over-States approach, this
one used to describe the 2PA spectra and is explained later.
1
6

Table 4 Permanent dipole momentum difference and transition dipole momentum for three compounds
studied in this work, in Debye unit.
Compounds
I
ꢹꢄꢙ
6.2
Δꢹꢄꢙ
9.0
ꢹꢙꢐ
7.8
ꢹꢙꢫ
-
II
III
7.3
8.4
5.1
4.2
2.3
3.2
3.7
5.0
Combining ꢹꢄꢙ and the 2PA spectrum, it is possible to determine additional information about the
molecules and charge distribution at different excited states by determining the magnitude of transition
dipoles moments from the higher excited states, ꢹꢙꢐ and ꢹꢙꢫ respectively. Additionaly, the difference of
permanent dipole momentum between the first excited state and the ground state, Δꢹꢄꢙ = ꢹꢙꢙ − ꢹ , can
ꢄꢄ
also be evaluated. These parameters were phenomenologically determined by employing Sum-Over-State
(
SOS) approach (Kamada et al., 2003; Neves et al., 2007) and, for this purpose, the two-photon
absorption spectra were phenomenologically adjusted (solid black line at Fig. 5) by using:
28ꢎπꢟ
ꢛꢐ
ꢐ
ꢐ
ꢐ
ꢐ
1
|ꢹ | Δꢹ Γ
|ꢹ | |ꢹ | Γ
ꢙꢐ ꢄꢙ ꢄꢐ
ꢄꢙ
ꢄꢙ ꢄꢙ
ꢼ
ꢽꢼ
ꢔꢢ
ꢚ
(ꢛ) =
ꢾ
+
ꢐꢑꢒ
(ꢠℎꢇ)ꢐ (ꢛꢄꢙ − ꢛ) + Γꢐ (ꢛꢄꢙ − 2ꢛ) + Γꢐ (ꢛꢄꢐ − 2ꢛ) + Γꢐ
ꢐ
ꢐ
ꢐ
5
ꢄꢙ ꢄꢙ ꢄꢐ
ꢐ
ꢐ
|
ꢹ | |ꢹ | Γ
ꢙꢫ ꢄꢙ ꢄꢫ
+
ꢿꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎꢎ(6)
ꢛꢄꢫ − 2ꢛ) + Γꢐ
ꢐ
(
ꢄꢫ
in which, ꢛꢄꢲ represents the transition frequency from ground state to excited state ꢇ; ꢇ can assume
values 1, 2 and 3. Γꢄꢲ is the damping constant corresponding to the same ꢇ transition, and ꢛ is the laser
frequency. In most cases, the damping constant for organic molecules in the UV-VIS is about 0.3 eV and
it was used in this work to all states. Terms inside of the brackets describe the states involved in the 2PA
spectra. The product of the transition dipole moments is related to the amplitude of the 2PA band, and ꢹꢄꢙ
is a fixed parameter obtained from the linear absorption. This makes the others transition dipoles to be
determined independent of each other. The parameters obtained with the SOS model combined with the
2
PA spectra (solid black line, Fig. 5) are listed at Table 3. It is important to say that the first electronic
state energy was obtained from the linear absorption spectra, which gave values of 3.5 eV for I, 3.8 eV
for II and 3.9 eV for III. The energy of the second 2PA band calculated to be of approximately 4.43 eV
was obtained from the 2PA spectra, related to a electronic state located at 280 nm. For the third band, we
used the energy of about 6 eV, related to an electronic state at approximately 205 nm.
Both, transition dipole moments and the difference of permanent dipole moment between first excited
state and ground state, are similar in magnitude to other chalcones already reported (Lemes et al., 2018;
Abegão et al., 2016), as well to small conjugated organic molecules, such as oxyzoles (Abegão et al.,
2
018). The highest value ofꢎΔꢹ , obtained for molecule I, explains the red shift observed in the 1PA and
ꢄꢙ
1
7

2
PA spectra, as well as the highest magnitude of molar absorptivity and 2PA cross section. It indicates
that the charges distribution is more delocalized on the ground and first excited states compared with
other two molecules. Also, the slightly higher planarity of I is in agreement with the increment of Δꢹꢄꢙ.
First hyperpolarizability values of the chalcone derivatives at 1064 nm were obtained with Hyper-
Rayleigh scattering measurements (HRS). Calibration of the experimental setup was performed by using
the well-known para-nitroaniline (pNA) compound dissolved in the same solvent as the chalcones
studied. HRS signals, illustrated as symbols in the inset of Fig. 6(a), have a quadratic dependence of the
generated nonlinear scattered signal, ꢓ(2ꢛ), at 532 nm as a function of the laser intensity, ꢓ(ꢛ), at 1064
nm. The inset also depicts for sample I distinct quadratic results (different colors) which are related to
different solute concentrations. Solid lines represent the best second order polynomial fittings. All other
samples and pNA standard molecule have shown similar graphics.
2
Figure 6 Linear dependence of I(2ω)/I (ω) as function of the molecular concentrations for pNA
(
squares) and chalcone derivatives: I (green square), (wine triangles) and III (red circles). Lines represent
the best linear fits. The inset, in (a), represents the first hyperpolarizability scattering signals as a function
of the pump intensity for distinct molar concentrations of sample III. Lines are the best second order
polynomial fits. Similar curves were obtained for the other compounds. The inset, in (b), depicts the
calculated β values for all compounds and pNA.
ꢐ
With the quadratic coefficient obtained by fitting ꢓ(2ꢛ) versus ꢓ (ꢛ) following Eq. (3), a linear
dependence of this coefficient as a function of the molecular concentration is observed. Figures 6(a) and
ꢐ
(
b) display ꢓ(2ꢛ)/ꢓ (ꢛ) (open symbols) as a function of the concentration for the derivatives I-III and
pNA. Solid lines represent the best linear fit, in which the angular coefficients were used to determine β
1
8

values by using Eq. (4). The value of βpNA is known from the literature. One can see that the linear fits
have different slope comparing each sample with pNA. pNA shows a greater slope comparing to I-III;
thus it is expected that β´s for all three samples are smaller than the standard sample. From the inset of
Fig. 6(b), it is possible to see, as column graphic, the experimentally calculated first hyperpolarizablity
values of all samples studied. β values of the three compounds are very similar, in which compound III
has the lower value. In general, the first hyperpolarizabilities of these compounds are in agreement with
other chalcone derivatives found in the literature (Vaz et al., 2016; Custodio, D’Oliveira et al., 2019).
The order of magnitude of the first hyperpolarizabilities (ꢦ) of all three chalcones derivatives can be
predicted by knowing ꢹꢄꢙ and ∆ꢹꢄꢙ values. The greater these quantities are, the higher the incoherent
optical second harmonic generation is. Thus, ꢦ can be estimated employing a simplified two-level model
approach (Lemes et al., 2018). It consists of, firstly, determining static first-order hyperpolarizability ꢦꢄ
by:
ꢫ ꣀꣁꢗꣂꢋ∙∆ꣁꢗꣂ
ꣃ
ꢦꢄ(0;0,0, ) = ꢐ
(7),
(ℏ꣄ꢗꣂ)ꢋ
in which, ℏꢛꢄꢙ is the energy of the first electronic transition obtained from the linear absorption spectrum
3.5 eV for I, 3.8 eV for II and 3.9 eV for III). The optical frequency dispersion (ꢛ) is taken into account
(
in order to evaluate the dynamical ꢦ by employing the undamped two-level model (Oudar, 1977; Campo
et al., 2008; Orr & Ward, 1971), which is enhanced by the proximity of the electronic resonance
(
resonance enhancement). The dynamical ꢦ is estimated by:
꣆
꣄
ꢗꣂ
ꢦꢐꣅꢩ(−2ꢛ; ꢛ, ꢛ) = ꣀ꣄ꢋ
ꢦꢄ
(8).
ꢉꢢ꣄ ꣃꣀ꣄ ꢉ꣄ꢋꣃ
ꢋ
ꢋ
ꢗꣂ
ꢗꣂ
The estimated values for dynamical ꢦꢐꣅꢩ were calculated at 1064 nm (~ 1.17 eV) and are of the same
order of magnitude for I-III. For compound I, which has the highest ∆ꢹ , ꢦꢐꣅꢩ(2ꢛ) has a value of
ꢄꢙ
-30
5
about 30 x10 cm /esu. Compounds II and III have values of ꢦꢐꣅꢩ(2ꢛ) smaller than compound I, of
-30
5
-30
5
about 21 x10 cm /esu and 19 x10 cm /esu respectively, because the difference between the excited
and ground state permanent dipole moments gives a smaller number than for I. In Figure 7, one can see
the estimated values obtained by using the simplified undamped model compared with the experimental
for all three studied samples, the error bars are considered to be of about 15%, due to laser intensity
fluctuation.
1
9

Figure 7 Estimated dynamic first-order hyperpolarizability by the simplified undamped model
compared to the experimental of all five studied compounds.
The experimental values obtained for I-III are of the same order of magnitude to the estimated
values, obtained from an undamped two-level model (Eq. 8). Considering experimental error, we can
state that β values of compound II and III are identical when compared to their respective estimated
values, showing that the parameters obtained with one- and two-photon absorption are in agreement with
the HRS signal. However, the measured β for compound I is 30% lower than that from the estimated
β
2LM. One explanation for this difference is associated to the energy of the lower absorption band.
For this molecule, the energy of the transition is reduced because of the redshift in the absorption
band. The energy value is part of Eqs. 7 and 8 as the denominator. Also, in Eq. 8 the dispersion
term, which enhances the effect due to the proximity of the transition, is also influenced by this
energy. With a redshift, the effect at 1064 nm is overestimated by the undamped two-level model.
However, if the error bar of the measurement is considered (about 15%), all values, for measured and
estimated ones, are considered statistical identical.
3
.3. Thermal characterization
The thermal behaviour of the crystalline compounds I, II and III was studied by a combination of
DSC, TGA and HSM techniques, and the results are presented in Figure 8. Both I, II and III are stable
between 25 and 130 ºC and their DSC curves exhibit endothermic melting peaks between 130 and 160 °C.
DSC curves of I and III are characterized by a single endothermic melting peak at 137.66 °C (Tonset
=
1
31.47 °C) and 157.63 °C (Tonset = 149.03 °C), respectively, which were attributed to the fusion of the
samples. Meanwhile, in DSC curves of compounds I and III, over 320 °C, exothermic events can be
observed; for III there is a clear exothermic peak at 328.25 °C (Tonset = 316.13 °C). In both cases these
peaks are attributed to the decomposition of the samples. These values agree with the gradual mass loss
2
0

that occurs in the TGA curves which begins around 260 °C (Tonset = 264.85 °C for I and Tonset = 283.22 °C
for III).
Figure 8 Thermal analysis. DSC, TGA curves and Hot-stage microscopy images of compounds I, II and
III, respectively.
The melting point of II is assigned to dual endothermic peaks at 149.26 °C and 155.47 °C (Tonset
44.17 °C) in the DSC curve. Unlike I and III, compound II presents a new endothermic-like pattern
over 280 °C, related to decomposition of the sample. This event is accompanied by the thermal
decomposition of the sample because of a gradual mass loss in the TGA curve up to 280 °C (Tonset
87.08 °C) can be observed. In comparison, compound I has the lowest thermal stability. HSM was
=
1
=
2
also performed in order to visualize the thermal events described above. Although HSM and
DSC/TGA experiments were performed under different atmospheres, the results are in good
agreement to each other. From HSM images (Fig. 8), it is possible to see that I, II and III crystals
undergo fusion at around 138 °C, 153 °C and 160 °C, respectively. The images also show the
beginning and complete melting of the crystals which are in agreement to DSC curves. It is worth to
2
1

mention that, according to DSC curves, there is evidence of other peaks that could be associated with
different phase transitions such as evaporation, but such behaviour was not observed in HSM.
4
. Conclusion
The three sulphonamide chalcone derivatives discussed here have a common backbone with different
substituents at para position of ring B. Compound I crystallizes in monoclinic system whereas the crystal
packing of II and III are triclinic. I, II, and III
because there is an angle of 16.37° between the planes of ring A and B. The effect of halogen
substituents changing, chlorine (II) by bromine (III) can be noticed in III due to the greatest angle
α could be consider planar molecules while IIIω is not,
α
formed by the A and B rings. Finally, C–H⋯O interactions dominates the packing of these compounds.
All compounds form dimers and arrangements where two accepting sites share one donor atom.
Nonlinear optical properties showed that the atoms or group added to the main structure of chalcone
studied do not modify significantly values of β nor σ2PA. σ2PA. The spectrum obtained shown that the first
excited state is permitted both by 1PA and 2PA, indicating that there is an asymmetric charge distribution
along the π-conjugated molecule structure. σ2PA spectra of compounds II and III show an excited state
that is permitted by 2PA. NLO properties of compounds I-III agree with other chalcones previously
studied, which indicates that adding the benzenossulfonyl group does not influence these properties.
Comparing HRS experimental results and theoretical model, estimated and experimental β values
obtained are in good agreement. Considering the similar experimental values for different substituents,
these results motivate further investigation on substituent-based optical properties for other sulfonamide-
chalcone hybrids.
5
. Acknowledgements
The authors gratefully acknowledge the financial support of the Conselho Nacional de desenvolvimento
Científico e Tecnológico (CNPq), Fundação de Amparo à Pesquisa do Estado de Goiás (FAPEG),
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP – Brazil; Grants 2016/20886-1 and
2
018/11283-7), INCT-FOTÔNICA Army Research Laboratory W911NF-17-1-0123 and Air Force Office
of Scientific Research (FA9550-12-1-00258). We also thank to Coordenação de Aperfeiçoamento de
Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001 for the financial support.
2
2

References
Abegão, L. M. G., Fonseca, R. D., Ramos, T. N., Mahuteau-Betzer, F., Piguel, S., Joatan R., J.,
Mendonça, C. R., Canuto, S., Silva, D. L. & De Boni, L. (2018). J. Phys. Chem. C. 122, 10526–
10534.
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. & Rodrigues, J. J. (2016). Chem.
Phys. Lett. 648, 91–96.
Allen, F. H. (2002). Acta Crystallogr. Sect. B Struct. Sci. 58, 380–388.
Bruker (2012). Apex 2. Bruker AXS Inc., Madison, Wisconsin, USA. [Older versions (pre-1997) should
refer to Siemens Analytical X-ray Instruments Inc. instead of Bruker AXS.
Campo, J., Wenseleers, W., Goovaerts, E., Szablewski, M. & Cross, G. H. (2008). J. Phys. Chem. C. 112,
287–296.
Castro, M. R. C. de, Aragão, A. Q., Napolitano, H. B., Noda-Perez, C. & Martins, F. T. (2013). Acta
Crystallogr. Sect. C Cryst. Struct. Commun. 69, 267–272.
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. (2016). J. Braz. Chem. Soc. 27, 884–898.
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. (2020). Arab. J. Chem. 13, 1345-1354
Chandra Shekhara Shetty, T., Raghavendra, S., Chidan Kumar, C. S., Naveen, S., Maidur, S. R., Patil, P.
S., Chandraju, S., Ananthnag, G. S. & Dharmaprakash, S. M. (2018). Opt. Mater. (Amst). 86, 138–
147.
Clays, K. & Persoons, A. (1992). Rev. Sci. Instrum. 63, 3285–3289.
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. (2019). J. Phys. Chem. C. 123, 5931–5941.
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. & Napolitano, H. B. (2019). J. Mol. Struct. 1175,
389–397.
Custodio, J., Michelini, L., Castro, M., Fonseca Vaz, W., Neves, B. J., Cravo, P., Barreto, F., de Moraes,
M. O., Perez, C. & Napolitano, H. (2018). New J. Chem. 42, 3426-3434.
D’silva, E. D., Podagatlapalli, G. K., Venugopal Rao, S. & Dharmaprakash, S. M. (2012). Mater. Res.
2
3

Bull. 47, 3552–3557.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl.
Crystallogr. 42, 339–341.
Franzen, P. L., Misoguti, L. & Zilio, S. C. (2008). Appl. Opt. 47, 1443.
Göppert‐ Mayer, M. (2009). Ann. Der Phisik. 18, 466–479.
Govindasamy, P. & Gunasekaran, S. (2015). J. Mol. Struct. 1081, 96–109.
Groom, C. R. & Allen, F. H. (2014). Angew. Chemie - Int. Ed. 53, 662–671.
Kamada, K., Ohta, K., Iwase, Y. & Kondo, K. (2003). Chem. Phys. Lett. 372, 386–393.
Kamal, A., Mallareddy, A., Suresh, P., Shaik, T. B., Lakshma Nayak, V., Kishor, C., Shetti, R. V. C. R.
N. C., Sankara Rao, N., Tamboli, J. R., Ramakrishna, S. & Addlagatta, A. (2012). Bioorganic Med.
Chem. 20, 3480–3492.
Kumar, P. C. R., Ravindrachary, V., Janardhana, K., Manjunath, H. R., Karegouda, P., Crasta, V. &
Sridhar, M. A. (2011). J. Mol. Struct. 1005, 1–7.
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., Souza, M. A. R.,
Mendonça, C. R., Gonçalves, P. J., de Boni, L., da Fonseca, T. L. & da Silva Junior, N. J. (2018).
Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 204, 685–695.
Lin, Y., Zhou, Y., Flavin, M. T., Zhou, L., Nie, W. & Chen, F. (2002). Bioorganic Med. Chem. 10. 10,
2795–2802.
Macrae, C. F., Bruno, I. J., Chisholm, J. a., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge,
L., Taylor, R., van de Streek, J. & Wood, P. a. (2008). J. Appl. Crystallogr. 41, 466–470.
Mahapatra, D. K. & Bharti, S. K. (2016). Life Sci. 148, 154–172.
Makhlouf, M. M., Radwan, A. S. & Ghazal, B. (2018). Appl. Surf. Sci. 452, 337–351.
Menezes, A. P., Jayarama, A. & Ng, S. W. (2015). J. Mol. Struct. 1088, 85–94.
Nardelli, M. (1995). J. Appl. Crystallogr. 28, 659–659.
Neves, U. M., De Boni, L., Ye, Z., Bu, X. R. & Mendonça, C. R. (2007). Chem. Phys. Lett. 441, 221–225.
Onsager, L. (1936). J. Am. Chem. Soc. 58, 1486–1493.
Orr, B. J. & Ward, J. F. (1971). Mol. Phys. 20, 513–526.
2
4

Oudar, J. L. (1977). J. Chem. Phys. 67, 446–457.
Raźna, J., Hodge, P., West, D. & Kucharski, S. (1999). J. Mater. Chem. 9, 1693–1698.
Rigaku, O. D. (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.
Sarojini, K., Krishnan, H., Kanakam, C. C. & Muthu, S. (2013). Spectrochim. Acta Part A Mol. Biomol.
Spectrosc. 108, 159–170.
Seo, W. D., Ryu, Y. B., Curtis-Long, M. J., Lee, C. W., Ryu, H. W., Jang, K. C. & Park, K. H. (2010).
Eur. J. Med. Chem. 45, 2010–2017.
Sheik-Bahae, M., Said, A. A., Wei, T.-H., Hagan, D. J. & Stryland, E. W. Van (1990). IEEE J. Quantum
Electron. 26, 760–769.
Sheldrick, G. (2008). Acta Crystallogr. Sect. A. 64, 112–122.
Sheldrick, G. M. (2015). Acta Crystallogr. Sect. A Found. Adv. 71, 3–8.
Singh, P., Anand, A. & Kumar, V. (2014). Eur. J. Med. Chem. 85, 758–777.
Spek, A. L. (2009). Acta Crystallogr. Sect. D. 65, 148–155.
Tajuddeen, N., Isah, M. B., Suleiman, M. A., van Heerden, F. R. & Ibrahim, M. A. (2018). Int. J.
Antimicrob. Agents. 51, 311–318.
Vaz, W. F., Custodio, J. M. F., Silveira, R. G., Castro, A. N., Campos, E. M., Anjos, M. M., Oliveira, G.
R., Valverde, C. & Napolitano, H. B. (2016). RSC Adv. 6, 79215–79227.
Zhai, L., Chen, M., Blom, J., Theander, T. G. & Kharazmi, A. (1999). J. Antimicrob. Chemother. 43,
793–803.
2
5

Highlights
•
•
A set of three new sulfonamide chalcones was synthesized;
Their chemical structures were analyzed from SCXRD and were found to be different
from each other;
•
NLO properties of the synthesized compounds were not affected by the structural
differences;

Declaration of interests
☒
The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐
The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: