PCCP

PAPER

A comprehensive study on the photophysical and

Cite this: Phys. Chem. Chem. Phys.,
2022, 24, 21927
non-linear optical properties of thienyl-chalcone
derivatives†
Qin Ai Wong, *a Ching Kheng Quah, *a Xin Ai Wong,b Yip-Foo Win,c
Huey Chong Kwong,a Parutagouda Shankaragouda Patil, d
Neelamma B. Gummagole and Venugopal Rao S. f

Received 10th May 2022,
Accepted 13th August 2022
DOI: 10.1039/d2cp02127g
rsc.li/pccp
The impact of the substitutional position of the chorine atom on the non-linear optical (NLO) response
of chalcone derivatives is reported in this paper. Two thienyl-chalcone derivatives, (E)-3-(2,4-dichloro-
phenyl)-1-(2,5-dichlorothiophen-3-yl)prop-2-en-1-one (3A25D2) and (E)-3-(2,6-dichloro-phenyl)-1-
(2,5-dichlorothiophen-3-yl)prop-2-en-1-one (3A25D4), are synthesized, and their crystal structures were
determined by single-crystal X-ray diffraction analysis. The photophysical and third-order NLO
properties of 3A25D2 and 3A25D4 were investigated experimentally and computationally. The third-
order NLO properties of 3A25D2 and 3A25D4 dissolved in N,N-dimethylformamide (DMF) were studied
using Z-scan technique with 800 nm, 70 femtosecond (fs) pulses, and 532 nm continuous wave (CW)
laser excitation. Closed aperture data recorded with fs pulses revealed positive non-linearity of both the
compounds, while a strong negative non-linearity was observed in the CW regime. Open aperture data
revealed that both the compounds exhibit positive non-linear absorption in fs pulsed and CW domains.
Several wave function analysis methods, such as the inter-fragment charge transfer (IFCT) analysis,
hole–electron analysis, (hyper)polarizability density analysis, and decomposition of the (hyper)polarizability
contribution by numerical integration, were carried out to study the optical properties and charge transfer
mechanism. In addition, the influence of the medium (liquid and crystalline) and external field wavelength
on the optical properties of the two molecules were analyzed. Thermal and electronic contributions
toward NLO properties were studied experimentally. The theoretically calculated cubic hyperpolarizability
g(o; o, o, o) in liquid for 3A25D2 and 3A25D4 were 4.69  1034 and 2.68  1034 esu, whereas the
corresponding femtosecond regime Z-scan results gave 4.35  1034 and 3.78  1034 esu, respectively.

1. Introduction fast response, ease of molecular design, and the advantage of

high transmission at low intensity for fundamental optical
Organic non-linear optical (NLO) materials play an important frequencies well below the bandgap frequency.1 In contrast,
role in fields such as photonics and optoelectronics due to their inorganic NLO materials are costly and relatively hard to be
a
integrated into photonic materials. The functional modules,
Pusat Pengajian Sains Fizik, Universiti Sains Malaysia, 11800 USM Pulau Pinang,
Malaysia. E-mail: ckquah@usm.my, qinai940224@gmail.com
e.g., electron donor, p-conjugated linker, or electron acceptor,
b
Department of Chemistry, Faculty of Science, Universiti Malaya, Kuala Lumpur are generally altered to tailor the photophysical and NLO
50603, Malaysia properties of organic compounds.2–5 A chalcone is constructed
c
Department of Chemical Science, Faculty of Science, Universiti Tunku Abdul Rahman, by two aromatic rings connected through an electron-acceptor
Perak Campus, Jalan Universiti, Bandar Barat, 31900 Kampar, Perak, Malaysia
d
a,b-unsaturated carbonyl system, and the functionalization of
Department of Physics, B.L.D.E. Association’s S.B. Arts and K.C.P. Science College,
Vijayapura 586103, Karnataka, India
chalcones by different electron-donor or acceptor substituents,
e
Department of Physics, K.L.E Institute of Technology, Opposite Airport, Gokul, Hubballi allowing charge transfer within the molecule, hence leading to
580027, Karnataka, India noticeable optical non-linearity. Several chalcone derivatives
f
Advanced Centre of Research in High Energy Materials (ACRHEM), University of have been investigated theoretically and experimentally for
Hyderabad, Hyderabad 500046, India
their NLO properties.6–12
† Electronic supplementary information (ESI) available: Full details of the struc-
ture determinations of compounds 3A25D2 and 3A25D4. CCDC 1952930 and
Besides the electron-donating/withdrawing strength of sub-
1952931. For ESI and crystallographic data in CIF or other electronic format see stitutional group(s), molecular aggregation was reported to
DOI: https://doi.org/10.1039/d2cp02127g enhance the NLO property of their individual molecules.13–18

This journal is © the Owner Societies 2022 Phys. Chem. Chem. Phys., 2022, 24, 21927–21953 | 21927
Paper
The molecular aggregation interplayed via the intermolecular
interactions, i.e., dipole–dipole interaction, p–p stacking,
hydrogen bonding, or halogen bonding.19 Virkki et al. reported
the non-linear responses of azobenzene chromophores increased
in association with the stronger halogen bond.20 Virkki et al.
reported that ‘‘the halogen-bonded supramolecular system is
superior to a hydrogen-bonded one even when the bonding
strengths are essentially equal’’, i.e., halogen bonding leads to
the enhancement of NLO in poled supramolecular polymers.21
Yushina et al. computed the second-order susceptibilities (w(2)) of
2-iodo-3-hydroxypyridine polymorphs and found linear correla-
tion between the lengths of halogen bonds and the calculated
w(2).22 The high electron-affinity of the halogen atom leads to the
attraction of electrons in the C–X bond; hence, the carbon atom
bears a partial positive charge, and the halogen atom bears a
partial negative charge.23 The polar covalent bond results in
molecular polarity and thereby manifold NLO property. This
paper presents the synthesized and characterization of two
chalcone derivatives compounds, namely, (E)-3-(2,4-dichloro-
phenyl)-1-(2,5-dichlorothiophen-3-yl)prop-2-en-1-one (3A25D2)
and (E)-3-(2,6-dichloro-phenyl)-1-(2,5-dichlorothiophen-3-yl)prop-
2-en-1-one (3A25D4), which possess the chlorine moiety at the
2,4- and 2,6-positions of the phenyl ring. Both compounds were
characterized from single-crystal X-ray diffraction and spectro-
scopic analyses. The intermolecular interactions among crystal
packing were investigated through Hirshfeld-surface analysis.
The cubic (second) hyperpolarizability, g, is the third-order
electric susceptibility per unit volume.24 The third-order NLO
effect is the lowest order NLO response apart from the second-
order NLO effect, which is restricted to non-centrosymmetric
symmetry.25 The nonlinear optical polarizabilities of various
frequency mixing schemes can be determined via the real and
imaginary parts of the non-linear susceptibility, w, which are related
to the non-linear refractive index coefficient (n2) and non-linear
absorption coefficient (a2), respectively (see Appendix).26 Currently,
the most popular techniques for the determination of the cubic
NLO properties of molecules are a third-harmonic generation
(THG), Z-scan, and degenerate four-wave mixing (DFWM), which
are derived from different frequency combinations.27 Among them,
the Z-scan technique is the simplest experimental arrangement
with high sensitivity, providing information about the real and
imaginary parts as well as the sign of g(o; o, o, o).28 This
technique measures two technologically relevant NLO parameters
of a sample—the non-linear refractive index coefficient and the
non-linear absorption coefficient.29 Recently, most of the research-
ers have measured the optical properties of chalcone derivatives by
Z-scan techniques in the solution forms30–32 and under one con-
dition of laser pumping.33–35 In this paper, we have studied the
optical non-linearities of two chalcone derivatives under the con-
ditions of pulsed (femtosecond) and continuous wave (CW) pump-
ing. Significant variations are observed in the non-linearity when
the pump source is switched from pulsed to CW.
This paper includes the theoretical calculations based on the
density functional theory (DFT) method to study the optical
properties. There are numerous computational studies regarding
the solvent effect on the NLO of molecules,36–42 however, the
21928 | Phys. Chem. Chem. Phys., 2022, 24, 21927–21953
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comparison of the NLO properties between (i) vacuum, (ii) liquid,
and (iii) crystalline environments is yet to be reported. In this
paper, the photophysical and non-linear properties of 3A25D2
and 3A25D4 molecules were calculated in different environ-
ments, namely, vacuum, polarizable continuum model as the
solvent model, and supramolecular approach as the crystalline
environment, and in-depth discussion has been carried out. The
computed electronic absorption spectrum and cubic hyperpo-
larizability results are compared to the experimental data. The
effects of external field wavelength on NLO were studied theo-
retically. We also conducted theoretical studies for the aroma-
ticity, electron delocalization, and vibration spectra, which are
important molecular characteristics at the electronic level.
2. Experimental
2.1. Characterization
The NMR spectra were recorded on a JEOL JNM-ECX 400
FT-NMR spectrometer in deuterated chloroform (CDCl3) with
tetramethylsilane (TMS) as the internal standard. The 1H and
13
C NMR spectra were measured at frequencies of 400 MHz and
100 MHz, respectively. The FT-IR spectra were obtained in the
range of 4000–450 cm1 using a PerkinElmer Spectrum 400
with ATR technique. The UV-Vis absorption spectra were mea-
sured in 1  104 M of N,N-dimethylformamide (DMF) solution
by a Varian Cary 5000 UV-Vis-NIR spectrophotometer with
10 mm quartz cells.
Single-crystal X-ray analyses was carried out using a Bruker
APEX II DUO CCD area detector diffractometer with a fine-focus
sealed tube graphite-monochromated Mo Ka radiation (0.71073 Å).
The collected raw data were reduced using the SAINT program,43
and empirical absorption correction is applied using the SADABS
program.43 The structures were solved by direct methods and
refined by full-matrix least-squares techniques using the SHELXTL
software package.44,45 All non-hydrogen atoms were refined aniso-
tropically. Hydrogen atoms were placed geometrically and refined
using a riding model with Uiso = 1.2 or 1.5 Ueq (C). Molecular
graphics and publications materials were prepared by OLEX2,46
Mercury,47 and PLATON.48 Hirshfeld atom refinement (HAR) was
implemented to optimize the H-bonded length of the crystal
structure relative to the independent atom model (IAM) by Olex2:
NoSpherA2 (Non-spherical atoms in Olex2)49,50 with an ORCA
version 4.2.1 program at the B3LYP/6-311G(d,p) level.51 The wave-
function output was used to perform charge distribution and
electrostatic potential calculations.
2.2. Computational details
Hirshfeld surface analysis and 2D fingerprint plots were pro-
duced using the CrystalExplorer 3.1 program.52,53 TONTO
application was employed to calculate the Hirshfeld surface
with the DFT method at the B3LYP/6-311G(d,p) level.54,55 dnorm,
curvedness, and shape index surface were mapped in the range
of 0.100–1.100 Å, 4.000–0.400 Å, and 1.000 Å, respectively.
Energy frameworks calculations were performed using the
CrystalExplorer 17 program56 at the B3LYP/6-31G(d,p) level of
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PCCP
Fig. 1 Model of the supramolecular approach for (a) 3A25D2 and (b) 3A25D4 compounds. The asymmetric unit at the center (magenta spacefill style) is
embedded by a molecular shell (first layer: cyan ball and stick style; second layer: capped stick style).
theory, where the total interaction energy (Etot) relative to the
reference molecule is given in terms of four components—
electrostatic (Eele), polarization (Epol), dispersion (Edip), and
exchange–repulsion (Erep) with scale factors of 1.057, 0.740,
0.871, and 0.618,56 respectively.
Gaussian 09 software package57 and Gaussview 5.058 are
used for quantum chemical calculations with the functional
B3LYP using the 6-311++G(d,p) basis set. The computational
linear and non-linear optical properties of 3A25D2 and 3A25D4
crystals were evaluated in (i) vacuum, (ii) liquid, and (iii) crystal-
line environments. The optimization processes are as follows.
(i) The initial geometries were retrieved from the crystal-
lographic data, which normalized the X–H bond lengths by the
Mercury program and were fully optimized in vacuum,
(ii) A similar procedure of step (i) within the solvent reaction
field of the DMF solution (e = 37.219) via Integral Equation
Formalism Variant Polarizable Continuum Model (IEFPCM), and
(iii) The supramolecular approach was used, where the
asymmetric unit of title molecules is embedded in a crystalline
environment (double layer of molecular shell) (Fig. 1). The
atoms of the molecular shell were modelled as a partial atomic
charge obtained using the CHELPG scheme. Then, these atoms
were replaced with its partial atomic charge previously obtained,
and the hydrogen atoms of the central molecule were optimized.
The optimized molecules were utilized for molecular (hyper)-
polarizabilities (using coupled-perturbed Kohn–Sham (CPKS)
method) and excitation energy calculation (using time-dependent
density functional theory (TD-DFT) method). Each calculation was
carried out in distinct environments, i.e., (i) vacuum phase, (ii) non-
equilibrium liquid with external iteration approach, and (iii)
supramolecular approach. The Grimme’s third-generation disper-
sion with Becke–Johnson damping (D3BJ) correction was included
in crystalline DFT calculations. The information of (hyper)polariz-
abilities was parsed out by analytical third energy derivatives, as
implemented in the Multiwfn 3.8 code.59 The isosurface maps and
real space functions were rendered via Visual Molecular Dynamic
(VMD) software.60 The detailed formulas for molecular (hyper)po-
larizabilities are given in the ESI.†
In order to compare with the experimental FT-IR and NMR
results, the vacuum phase-optimized molecule (calculated in
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Paper
step i) was employed for spectroscopic analysis. The vibrational
frequencies were assigned using potential energy distribution
(PED) analysis by the VEDA 4 program.61 The computed
chemical shifts were carried out using the GIAO approach with
solvent chloroform and referenced with respect to the standard
TMS, which is optimized at the B3LYP/6-311+G(2d,p) level.
2.3. Z-Scan studies
Third-order non-linear optical susceptibility, w(3)(o; o, o,
o), are measured experimentally by open and closed aperture
Z-scan technique.28 The Z-scan technique is a simple method
for measuring two technologically relevant NLO parameters of a
sample, i.e., non-linear refractive index coefficient (n2) and non-
linear absorption coefficient (a2). This technique involves the
scanning of the sample along the propagation axis of the
incident Gaussian laser beam (z-direction). The translation of
the sample creates varying light intensities. A plano-convex lens
was used to focus the laser beam and a computer-controlled
translation stage was used to move the sample. The transmittance
of the sample was evaluated as a function of the sample position
(z) measured with respect to the focal plane. The non-linear
refraction was observed through an adjustment to achieve 40%
of the power transmitted through the sample by placing a finite
aperture in the far-field (closed-aperture Z-scan), whereas non-
linear absorption was observed by removing the aperture (open-
aperture Z-scan).
In this study, the use of CW lasers may lead to thermal
artifacts and in the present work, this issue has been addressed
by comparing the results between the 532 nm continuous wave
(CW) laser and the 800 nm femtosecond (fs) pulse laser. The
samples were dissolved in DMF solution and contained in a
quartz cuvette with 1 mm thickness (L) for all the experiments.
The first setup was made from the fs pulse laser, which is
produced by a Ti–sapphire regenerative amplifier (Libra, coher-
ent) operated at a wavelength (l) of 800 nm with a 70 fs pulse
width and a 1 kHz repetition rate. The Z-scan experiments were
carried out with typically 0.1–0.2 mW input power with the
corresponding pulse energy being 0.1–0.2 mJ. The focal length
of the plano-convex lens was 20 cm. The beam waist (o0) of the
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Table 1 Experimental and calculated (DFT) 1H NMR chemical shifts (d in ppm) of 3A25D2 and 3A25D4

3A25D2 3A25D4
H Exp. (multiplicity, J) DFT Exp. (multiplicity, J) DFT
3 7.20 (s, 1H) 7.32 7.23–7.19 (t, 2H, J = 8.0 Hz) 7.33
6 7.36–7.32 (d, 1H, J = 16.0 Hz) 7.82 7.60–7.56 (d, 1H, J = 16.0 Hz) 7.95
7 8.08–8.04 (d, 1H, J = 16.0 Hz) 8.78 7.88–7.84 (d, 1H, J = 16.0 Hz) 8.48
10 7.46 (s, 1H) 7.60 7.39–7.37 (d, 2H, J = 8.0 Hz) 7.53
11 7.23–7.19 (t, 2H, J = 8.0 Hz) 7.36
12 7.30–7.28 (d, 1H, J = 8.0 Hz) 7.37 7.39–7.37 (d, 2H, J = 8.0 Hz) 7.51
13 7.64–7.62 (d, 1H, J = 8.0 Hz) 8.10
For 1H NMR data, s, d, and t refer to singlet, doublet, and triplet, respectively. Coupling constants in Hertz are given in parentheses.

2f l
focal spot was calculated through the relationship o0 ¼
pD
where D is the diameter of the incident beam (4 mm), and its
corresponding Rayleigh range (zR) was estimated to be 2.55 mm
using ZR = po02/l. The peak intensity at the focus (I0) was
estimated to be 182 GW cm2. The sample solution was
prepared at 5 mM concentration.
For evaluating the NLO properties at a wavelength of
532 nm, the CW diode-pumped solid-state (DPSS) laser with
200 mW output power and 1.2 mm s1 scan speed was used as a
light source. The concentration of the sample solution was
0.01 M. A lens with a 25 cm focal length was used to focus the
laser beam with a diameter of 7 mm. The I0 was 23.7 kW cm2
at the focal plane. The o0 and zR were determined to be 23.2 mm
and 3.17 mm, respectively. The thin sample approximation was
satisfied for both fs pulses and CW laser Z-scan experiment as
(400 MHz, CDCl3, d, ppm): 7.88–7.84 (d, 1H, J = 16.0 Hz, 7CH),
,
7.60–7.56 (d, 1H, J = 16.0 Hz, 6CH), 7.39–7.37 (d, 2H, J = 8.0 Hz,
10
CH & 12CH), 7.23–7.19 (t, 2H, J = 8.0 Hz, 3CH & 11CH); 13C NMR
(100 MHz, CDCl3, d, ppm): 183.41 (C5), 138.59 (C7), 137.31 (C1),
135.45 (C9), 135.45 (C13), 132.36 (C8), 132.16 (C2), 131.39 (C11),
130.24 (C3), 129.04 (C10), 129.04 (C12), 127.26 (C6), 127.18 (C4);
FT-IR (ATR (solid), n, cm1): 3109 (Th, C–H), 3086 (Ar, C–H),
1662 (CQO), 1602 (CQC), 1579, 1557 (Ar, CQC), 1524, 1425,
1363 (Th, CQC), 1079, 751(Ar, C–Cl), 973, 628, 521 (Th, C–Cl),
668 (C–S).
3. Results and discussion
3.1. NMR analysis
The H and 13C NMR spectra are shown in Fig. S1–S4 (see the
1

the sample thickness (L) is less than the Rayleigh range (zR). ESI†). The sequential assignments of protons and carbons was
carried out by means of DFT theoretical calculations (Tables 1
2.4. Synthesis and 2). The dH values obtained are 7.20–8.08 ppm for 3A25D2
Compounds 3A25D2 and 3A25D4 were synthesized according and 7.19–7.88 ppm for 3A25D4. Two vinylic trans protons
to Claisen–Schmidt condensation. 1-(2,5-Dichlorothiophen-3- (H6 and H7) were resolved as two doublets and easily differentiated
yl)ethan-1-one (0.28 g, 1.4 mmol) was added to a solution of by their coupling constant (J = 16.0 Hz). A downfield shift of
dichlorobenzaldehyde (2,4-positions for 3A25D2; 2,6-positions 0.02–0.38 ppm was discovered for the aryl protons from thienyl
for 3A25D4) (0.25 g, 1.4 mmol) in methanol (8 mL). The mixture and phenyl rings, which suggests the deshielding effect of
was catalyzed by an aqueous sodium hydroxide solution (15 M) electron-withdrawing Cl substitutions. The number of protons
and stirred vigorously for 6 hours at room temperature. The in both the compounds is in accordance with the postulated
crude product was rinsed with cold water, filtered, and then structure in terms of the integration value. In the 13C NMR
dried. A single crystal was grown by the evaporation technique. spectra, the alkene/aromatic carbon signals were observed in
(E)-3-(2,4-Dichloro-phenyl)-1-(2,5-dichlorothiophen-3-yl)prop-
2-en-1-one (3A25D2). Solvent for growing crystals: acetone– Table 2 Experimental and calculated (DFT) 13
C NMR chemical shifts (d in
methanol (1 : 3); yield 81%; m.p. 136 1C; 1H NMR (400 MHz, ppm) of 3A25D2 and 3A25D4
CDCl3, d, ppm): 8.08–8.04 (d, 1H, J = 16.0 Hz, 7CH), 7.65–7.62 (d,
3A25D2 3A25D4
1H, J = 8.0 Hz, 13CH), 7.46 (s, 1H, 10CH), 7.36–7.32 (d, 1H, J = 16.0
Hz, 6CH), 7.30–7.28 (d, 1H, J = 8.0 Hz, 12CH), 7.20 (s, 1H, 3CH); C Exp. DFT Exp. DFT
13
C NMR (100 MHz, CDCl3, d, ppm): 183.44 (C5), 139.89 (C7), 1 137.55 150.83 137.31 132.97
137.55 (C1), 136.99 (C9), 136.37 (C11), 131.76 (C8), 131.46 (C2), 2 131.46 145.90 132.16 146.02
3 127.75 133.18 127.26 132.97
130.33 (C13), 128.67 (C10), 127.75 (C3), 127.36 (C4), 127.23 (C12), 4 127.36 145.72 127.18 144.73
126.30 (C6); FT-IR (ATR (solid), n, cm1): 3112 (Th, C–H), 3093, 5 183.44 186.66 183.41 186.77
3068 (Ar, C–H), 1653 (CQO), 1599 (CQC), 1581, 1470, 1385 6 130.33 127.61 131.39 134.05
7 139.89 146.62 138.59 147.73
(Ar, CQC), 1520, 1424, 1360 (Th, CQC), 1107, 1048, 789, 657, 8 131.76 136.11 132.36 138.59
(Ar, C–Cl), 978, 598 (Th, C–Cl), 668 (C–S). 9 136.99 151.63 135.45 151.44
(E)-3-(2,6-Dichloro-phenyl)-1-(2,5-dichlorothiophen-3-yl)prop- 10 127.75 135.54 129.04 133.61
11 136.37 151.43 130.24 134.85
2-en-1-one (3A25D4). Solvent for growing crystals: dichloro- 12 126.30 131.98 129.04 134.25
methane–methanol (1 : 1); yield 79%; m.p. 142 1C; 1H NMR 13 128.67 133.32 135.45 148.14

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Table 3 Experimental and calculated (DFT) FT-IR vibration bands’ assignment (wavenumber in cm1)

3A25D2 3A25D4
DFT DFT
Band assignment Exp. Unscaled Scaled Exp. Unscaled Scaled
2
nC–H (sp , Th) 3112 3235 3099 3109 3235 3099
nC–H (sp2, En & Ph) 3093, 3068 3211, 3189 3076, 3055 3086 3211 3076
nCQO 1653 1713 1684 1662 1717 1688
nCQC (En) 1599 1638 1610 1602 1646 1618
nCQC (Ph) 1581, 1470, 1385 1617, 1496, 1415 1590, 1471, 1391 1579, 1557 1617, 1587 1590, 1560
nCQC (Th) 1520, 1424, 1360 1565, 1462, 1379 1538, 1437, 1356 1524, 1425, 1363 1565, 1463, 1375 1538, 1438, 1352
gC–H (trans) 1025 1026 1009 1024 1018 1001
nC–Cl (Th) 978, 598 991, 612 974, 602 973, 628, 521 991, 633, 532 974, 622, 523
nC–Cl (Ph) 1107, 1047, 789, 657 1118, 1063, 796, 666 1099, 1045, 782, 655 1079, 751 1100, 780 1081, 767
gC–H (Ph) 870, 806 884, 829 869, 815 772, 690 787, 710 774, 698
gC–H (Th) 859 866 851 852 865 850
nC–S 668 684 672 668 685 673
Th: thiophenyl ring; En: enone bridge; Ph: phenyl ring; n: stretching; g: out-of-plane bending.

the downfield region in the range of dC = 126–140 ppm experi- Table 4 Crystal data and refinement parameters for compounds 3A25D2
mentally and 128–152 ppm theoretically. The remarkable sig- and 3A25D4
nals with the highest chemical shift (183 ppm) are assigned to 3A25D2 3A25D4
carbonyl carbon (C5). The different dC values of the aromatic
CCDC deposition number 1952930 1952931
carbon C11 and C13 in the spectra of 3A25D2 and 3A25D4 reveal Molecular formula C13H6Cl4OS C13H6Cl4OS
the alternatively bound H/Cl in these two positions. For 3A25D4, Molecular weight 352.04 352.04
the carbon signals C9/C13 and C10/C12 were synced into 2 Crystal system Orthorhombic Monoclinic
Space group P212121 P21/n
signals due to the symmetric nature of the phenyl ring. a (Å) 3.9858 (7) 3.8532 (7)
b (Å) 13.451 (2) 14.632 (3)
3.2. FT-IR vibrational analysis c (Å) 25.545 (4) 24.278 (5)
b (1) 90 93.236 (3)
The experimental and calculated infrared spectra of 3A25D2 V (Å3) 1369.5 (4) 1366.7 (4)
and 3A25D4 are presented in Fig. S5 and S6 (see the ESI†). Z 4 4
Vibrational frequencies calculated above and below 2000 cm1 Dcalc (g cm3) 1.707 1.711
Crystal dimensions (mm) 0.34  0.23  0.05 0.46  0.10  0.06
were scaled by 0.958 and 0.983, respectively.62,63 The vibrational Crystal color, shape Plate, colorless Needle, brown
assignment of several main modes along with the observed and m (mm1) 1.00 1.00
calculated wavenumber are listed in Table 3. The scaled and Radiation, l (Å) Mo Ka, 0.71073 Mo Ka, 0.71073
Tmin, Tmax 0.672, 0.747 0.690, 0.777
observed frequencies show good agreement, confirming the Measured reflections 7501 17 830
functional groups and substituents of chalcone derivatives. hkl range 4 r h r 5 4 r h r 4
17 r k r 14 18 r k r 18
3.3. Single-crystal X-ray diffraction and Hirshfeld surface analysis 32 r l r 26 30 r l r 30
y limit (1) 1.6–27.0 1.6–27.0
The crystal data, data collection, and structure refinement Unique reflections 2968 2962
details of 3A25D2 and 3A25D4 are summarized in Table 4, and Observed reflections 2323 2315
Parameters 172 172
their asymmetric unit diagram is depicted in Fig. 2. Compounds Goodness of fit on F2 1.03 1.11
3A25D2 and 3A25D4 are crystallized in the non-centrosymmetric R, wR(F2) 0.040, 0.084 0.115, 0.050
orthorhombic space group P212121 and the centrosymmetric
monoclinic space group P21/n, respectively. The enone moiety
of both the structures adopts trans-(s-cis) conformation, indicated of 0.6456 Å and a maximum deviation of 1.2691 Å (Fig. 3). The
by the O1QC5–C6QC7 torsion angle of 1.1(7)1 and 7.8(6)1, and structure 3A25D2 exhibits an intramolecular C6–H6A  Cl1
the C5–C6QC7–C8 torsion angles of 179.5(4)1 and 177.1(3)1. hydrogen bond with the S6 graph set motif.
The dihedral angle between the constituent planar fragments The intermolecular interactions of 3A25D2 and 3A25D4 were
is relatively small for 3A25D2 compared with 3A25D4. The least- elucidated with Hirshfeld surface analysis and the associated
square plane of thienyl and phenyl rings forms a dihedral 2D fingerprint plots. The decomposition fingerprint plots facil-
angle of 12.1(2)1 for 3A25D2 and 31.97(9)1 for 3A25D4. The ities rapid comparison between the related molecules in the
a,b-unsaturated carbonyl moiety of 3A25D2 are syn-periplanar title crystals (Fig. 4 and Fig. S7, ESI†). Besides, the 3D-topology
to the thiophene and benzene rings by 12.5(3)1 and 0.4(3)1, energy framework is generated from the pairwise interaction
whereas the syn-clinal configuration is observed for 3A25D4 energies between the molecules within a representative cluster
with dihedral angles of 30.7(1)1 and 41.7(1)1, respectively. The from the crystal lattice.
large deviation in the conformation is revealed by the super- The role of halogen atoms is to direct the architecture
imposition of both the structures with molecular overlay RMSD of molecular crystal structures. The calculation of contact

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Paper
Fig. 2 The ORTEP diagram of the asymmetric unit of (a) 3A25D2 and (b) 3A25D4 shown in 50% probability displacement ellipsoids with labels for non-
hydrogen atoms.
Fig. 3 Molecular overlay diagram for non-hydrogen atoms excluding the
4-position and 6-position chlorine atom in 3A25D2 and 3A25D4,
respectively.
contributions to the relative Hirshfeld surface areas suggests
that the most prevalent interactions in the title compounds are
H  Cl/Cl  H contacts (20.7% and 28.0%) (Fig. 4b). However,
the H  Cl/Cl  H contact fingerprint plots are overly broad due
to the low angle contact and long distance relative to the van der
Waals (vdW) separation. Both crystals feature halogen bonds
that are shorter than the vdW separation, and the particularly
close contacts are highlighted via decomposition fingerprint
plots. The existence of the O1  Cl1 halogen bond for 3A25D2 is
shown clearly from the very sharp O  Cl/Cl  O fingerprint
spike at de + di C 3.10 Å (Fig. 4c). The dnorm surface of
3A25D2 (Fig. 5a) shows two relatively large distinctive red spots
in the regions of close O1 and Cl atoms. The O1  Cl1i halogen
bonds (3.131(3) Å) [symmetry code: (i) x, 1/2 + y, 3/2  z]
Fig. 4 (a) The 2D fingerprint plots and resolved into various intermolecular contacts: (b) H  Cl/Cl  H, (c) O  Cl/Cl  O, (d) Cl  Cl, and (e) C  C with
relative percentage contributions to the Hirshfeld surface area for 3A25D2 and 3A25D4.
21932 | Phys. Chem. Chem. Phys., 2022, 24, 21927–21953
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aggregate 21 helices propagating along the b-axis (Fig. 6). These
interactions are estimated to be 19.2 kJ mol1 for Etot (Fig. S8
and Table S1, ESI†). The 2D fingerprint plot for 3A25D4 features a
narrow green stripe on the diagonal of the plots, starting from de =
di C 1.72 Å due to the three-center Cl  Cl halogen bonds (Fig. 4d).
The Cl1 atom is involved in one symmetrical contact (Cl1  Cl1ii)
and one bent contact (Cl1  Cl4iii), where Cl1  Cl1 = 3.4586(15) Å,
+C1–Cl1  Cl1 = 128.54(12)1 and Cl1  Cl4 = 3.4833(14) Å,
+C1–Cl1  Cl4 = 113.73(11)1 and +C13–Cl4  Cl1 = 168.70(11)1 [symme-
try codes: (ii) 1  x, 1  y, 1  z; (iii) 2  x, 1  y, 1  z]. The three
small red spots on the dnorm surface of 3A25D4 near the Cl and Cl4
atoms are also indicative of the Cl  Cl halogen bonds (Fig. 4b).
The Cl  Cl halogen bonds between inversion-related molecules
assemble a zig-zag chain propagating along the a-axis (Fig. 7) with
an Etot of 9.7 and 7.4 kJ mol1 (Fig. S9 and Table S2, ESI†).
From the over distance (relative to vdW separation) of certain
characteristic patterns, there are no Cl  Cl contacts in 3A25D2
and no O  Cl contacts in 3A25D4, but C  C contacts occur in
all cases. C  C (i.e., p  p) close contacts is an evident from the
blue-green region on the fingerprint plots (Fig. 4e) centered at
de = di C 1.8 Å, which comprises 11.9% and 10.6% of the surface
area in 3A25D2 and 3A25D4, respectively. The adjacent blue and
red patches on the shape index surfaces (highlighted by dashed
circles in Fig. 8a) and the large flat region (green) (Fig. 8b) on
curved surfaces reveal the p  p stacking arrangement in the
crystal [3A25D2/3A25D4: Cg1  Cg1iv = 3.986(2)/3.853(2) Å,
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Fig. 5 Hirshfeld surfaces of (a) 3A25D2 and (b) 3A25D4 mapped with dnorm, highlighted the intermolecular halogen bonding motifs.

Fig. 6 Partial crystal packing of 3A25D2 with intramolecular C–H  Cl hydrogen bonds (orange dashed lines), intramolecular O  Cl halogen bonds
(blue dashed lines), and p  p interactions (magenta dashed lines).

Fig. 7 Partial crystal packing of 3A25D4 with intramolecular Cl  Cl halogen bonds (blue dashed lines) and p  p interactions (magenta dashed lines).

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Paper PCCP

Fig. 8 Hirshfeld surface (front and back views) mapped with (a) shape index and (b) curvedness for 3A25D2 and 3A25D4.

offset = 1.676/1.363 Å; Cg2  Cg2iv = 3.986(2)/3.853(2) Å, offset =
1.872/1.499 Å; Cg1 and Cg2 are the centroids of the S1/C1–C4
thienyl ring and the C8–C13 phenyl ring, respectively; symmetry
code: (iv) 1 + x, y, z]. The p  p contacts are found to be the
most stable interactions present in the crystal packing of
3A25D2 and 3A25D4 with an Etot of 49.5 and 50.6 kJ mol1,
respectively. An in-depth crystallographic investigation on
3A25D2 has been reported by Sanjeeva Murthy.64
3.4. Charge distribution and electrostatic potential
3.4.1. Charge distribution. Atomic Dipole Moment Corrected
Hirshfeld (ADCH)65 population can manifest the electron-donating
and accepting abilities of substituents. In order to define the
effects of para/ortho-Cl substituent for 3A25D2 and 3A25D4, the
entries in Table 5 contain the ADCH atomic charges (qADCH) for
3A25D2 and 3A25D4 along with the qADCH of (E)-3-(2-chlorophenyl)-
1-(2,5-dichlorothiophen-3-yl)prop-2-en-1-one (3C25D)66 (as a
comparison), which was reported by Sanjeeva Murthy et al.
and further HAR-refined. Some consensuses can be summarized
as follows.
(1) The electron-withdrawing ability of Cl atoms and carbo-
nyl groups are demonstrated by the negative qADCH, whereas the
sulphur of the thienyl group acts as an electron-donating due to
its positive qADCH.
(2) The variation in the fragmental charges for the dichlor-
othienyl ring and enone groups demonstrates that the atomic
charges are influenced by the conformation.
(3) A comparison of the fragment charges of dichlorophenyl
rings of the title molecules with the monochlorophenyl ring of
3C25D shows that the charge shifts induced by the para-Cl to
the phenyl ring are positive (DqADCH = 0.029), while by the ortho-
Cl are negative (DqADCH = 0.016).
These values show the influence of the substitutional position
on the charge distribution. The electron-withdrawing inductive
(–I) effect along the s bonds are dependent on the proximity, the
–I effect of the para position of chlorobenzene is less than that of
the ortho position. Therefore, the electron-releasing resonance
effect along the p-electron system appears to overcome the electron-
withdrawing inductive effect along the s bonds for the phenyl ring
in 3A25D2 and inversely in 3A25D4. This makes the para-Cl of
3A25D2 a donating group, while the ortho-Cl of 3A25D4 is a
withdrawing group.
3.4.2. Electrostatic potential (ESP). ESP plays a crucial role
in elucidating the natures of intermolecular interactions. Fig. 9
provides the ESP mapped on the molecular vdW surface (range:
0.03 a.u.) and surface extreme,67 in which the electrophilic
and nucleophilic reactive sites are displayed as red and blue
regions, respectively. To better understand the electrostatic

Table 5 Atomic dipole moment corrected Hirshfeld (ADCH) charges and the charges of the functional groups

Atom 3A25D2 3A25D4 3C25D Atom 3A25D2 3A25D4 3C25D

Cl1 0.018 0.009 0.022 H6A 0.071 0.216 0.065
Cl2 0.017 0.012 0.02 C7 0.080 0.016 0.099
Cl3 0.028 0.035 0.041 H7A 0.094 0.119 0.092
Cl4 0.063 0.352 C8 0.004 0.398 0.007
S1 0.093 0.178 0.108 C9 0.033 0.039 0.01
O1 0.289 0.269 0.291 C10 0.156 0.143 0.035
C1 0.073 0.036 0.099 H10A 0.131 0.123 0.074
C2 0.009 0.103 0.044 C11 0.122 0.062 0.103
C3 0.149 0.197 0.016 H11A 0.146 0.127
H3A 0.159 0.236 0.084 C12 0.279 0.576 0.1
C4 0.006 0.032 0.057 H12A 0.165 0.153 0.116
C5 0.173 0.254 0.188 C13 0.055 1.138 0.103
C6 0.093 0.391 0.029 H13A 0.094 0.124
Dichloro-thienyl ring 0.046 0.025 0.01 (Di/mono)chloro-phenyl ringa 0.078 0.033 0.062
Enone 0.124 0.055 0.074
a
Denotes the C6H3Cl2 part for 3A25D2 and 3A25D4, while the C6H4Cl part for 3C25D.

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PCCP Paper

Fig. 9 Electrostatic potential (ESP) mapped on the vdW surface (isosurface r = 0.001 a.u.) of (a) 3A25D2 and (b) 3A25D4 molecules. Minima and maxima
of ESP on the surface are drawn as magenta and cyan spheres with the corresponding ESP value in kcal mol1, respectively.

potential characteristic of the respective fragment of the mole-
cules (i.e., enone bridge, dichlorothienyl, and dichlorophenyl
rings), the quantitative molecular surface analysis module68 are
partition calculated and plotted in Fig. 10. For 3A25D2 and
3A25D4, the polar surface areas (|ESP| 4 10 kcal mol1) are
77.12 and 73.10 Å3, which occupy 23.95% and 23.20% of the
overall vdW surface, respectively. This reveals that the substitu-
tion of Cl at the para-position causes the molecule to be more
polar than that at the ortho-position. From the ESP maps, we
found that the negative areas of ESP are located around the side-
on portion of the Cl surface, while a small region of positive ESP
is localized at the outer tip of the Cl. The positive areas reveal
the chlorine’s positive s-hole, which can essentially form linear
interaction with the negative sites of another molecule.69 The
enone group constitutes a majority of vdW surfaces containing
larger negative ESP values (i.e., o10 kcal mol1) (Fig. 10). The
ESP maps also show that the lone pair of the carbonyl oxygen
leads to the global surface minima (about 33 kcal mol1),
reflecting the oxygen-forming interactions with Cl1 in the
3A25D2 crystal. The surface area with positive ESP for dichlor-
othienyl and dichlorophenyl rings are much larger than that
with negative ESP. These positive ESP regions mainly belong to
the sulphur and hydrogen atoms. The global surface maxima for
3A25D2 and 3A25D4 are +28.35 and +24.98 kcal mol1, which
correspond to the H13A and H11A atoms, respectively.
3.5. Experimental UV-vis spectroscopy
A larger non-linearity and a small linear absorption coefficient
(a0) are critical for optical devices because a high a0 can cause a
decline in the device performance and significant thermal loss.
The UV-Vis absorption spectra of compounds 3A25D2 and
3A25D4 are investigated in DMF solution with a concentration
of 1  104 M at room temperature (Fig. 11). The maximum
absorption peak induced by strong p - p* electronic transition
of the conjugated system is observed at 319 and 298 nm for
3A25D2 and 3A25D4, respectively. A small bathochromic shift
and a significant hyperchromic shift is displayed from 3A25D4
to 3A25D2, demonstrating that the relative positioning of the
chlorine group (ortho- or para-) at the phenyl ring induces a
change in the optical characteristics. The cut-off wavelength of
absorptions is about 400 nm, showing transparency in the entire
visible range similar to the reported chalcone derivatives70,71 and
hence assuring their suitability for optoelectronic applications.
The optical gap (Eg) is estimated from the Tauc plot extrapolation
using the following relation.
 1
a0 hv ¼ C hv  Eg 2 (1)
where C is a constant, h is Planck’s constant, v is the frequency of
the incident photons, and a0 is the optical absorption coefficient,
which is calculated with a = 2.303  (A/d), A is the absorbance and

Fig. 10 Surface area distribution of different ESP intervals on the vdW surface of 3A25D2 and 3A25D4 molecules. The partition between three fragments
is displayed in different colors (i.e., dichloro-thienyl ring: pink, enone bridge: green, and dichlorophenyl ring: blue).

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Paper PCCP

d is the thickness of the sample. The Tauc plots for both the
structures are shown in Fig. 11 (inset graph), and the Eg values
are deduced to be 3.50 eV and 3.67 eV.

3.6. Z-scan analysis

Fig. 11 UV-Vis absorption spectrum of 3A25D2 and 3A25D4 and Tauc
plot of the directly allowed energy band gaps (inset graphs).
3.6.1. Non-linear absorption (NLA) and non-linear refraction
(NLR). We conduct closed and open aperture Z-scan experiments
under both femtosecond (fs) pulses and continuous-wave (CW)
excitation to determine the non-linear coefficients and to better
understand the mechanisms for the observed optical non-
linearities. The normalized non-linear transmittance for both
compounds recorded using fs pulses (800 nm) and CW (532 nm)
lasers are presented in Fig. 12 and 13, respectively. The experi-
mental data are fitted by the Sheik Bahae’ model.28
The open aperture (OA) Z-scan data are fitted with the
eqn (A.1) (see the Appendix) to determine the non-linear absorp-
tion coefficient (a2) and the imaginary part of the third-order

Fig. 12 (a) Open aperture (OA) and (b) closed aperture (CA) Z-scan curves of 3A25D2 (green) and 3A25D4 (magenta) compounds at a concentration of
10 mM, under a 532 nm CW laser. The dotted lines denote the theoretical fits of eqn (A.4)–(A.8) while the symbols represent the experimental data.

Fig. 13 (a) Open aperture (OA) and (b) closed aperture (CA) Z-scan curves of 3A25D2 (green) and 3A25D4 (magenta) compounds at a concentration of
5 mM under a 800 nm fs pulsed laser. The dotted lines denote the theoretical fits of eqn (A.4)–(A.8) while the symbols represent the experimental data.

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5.07  1016
5.03  1016

8.59  1023
9.74  1023
sex (cm2)
9.30  1021
8.63  1021

4.25  1021
6.68  1021
sg (cm2)

4.82  107
7.16  107
s2 (GM)
22.92
21.13
4.35  1034
3.78  1034

1.76  1027
1.19  1026

Fig. 14 Plot of ln(1  TOA) vs. ln(I0) of 3A25D2 (green) and 3A25D4
g (esu)

(magenta) under CW laser illumination.

Non-linear optical parameters of 3A25D2 and 3A25D4 in DMF solution under fs pulsed (800 nm) and CW (532 nm) excitations

susceptibility I(w(3)(o; o, o, o)) (Table 6). The presence of a

4.39  1015
3.82  1015

3.56  108
2.40  107

valley at z = 0 in the OA scans implies positive non-linear

w(3) (esu)

absorption. The NLA is attributed to multiple-photon absorption

(MPA), excited-state absorption (ESA), free carrier absorption,
non-linear scattering, or a combination of these processes.72 The
efficiency of a molecule to transit from the ground-state to the
9.23  1016
8.51  1016
I (w(3)) (esu)

1.72  109
2.55  109

excited-state through the 2PA process is described by the 2PA

cross-section (s2). The values of s2 of 3A25D2 and 3A25D4 are
calculated by eqn (A.4). The plots of ln(1  TOA) vs. ln(I0) for
3A25D2 and 3A25D4 under CW domain, as shown in Fig. 14,
3.55  108
2.40  107

displays a straight trendline with a slope of approximate unity,

4.30  1015
3.72  1015
<(w(3)) (esu)

indicating that the main process NLA in the case of CW laser is

contributed from 2PA.73 However, the NLA observed at the fs
pulsed laser would be a result of the cumulative effects from ESA
and 2PA. The RSA induced by the ESA can be determined as the
6.80  1010

value of the excited-state absorption cross-section (sex), which is

4.59  109
n2 (cm2 W1)
8.23  1017
7.12  1017

greater than that of the ground-state absorption cross-section

(sg). The values of sex and sg are calculated by eqn (A.5) and (A.6)
and listed in Table 6. The condition of sex 4 sg is not met in the
CW Z-scan experiment but in the fs pulsed Z-scan experiment.
Thus, we may propose that the non-linear absorption for both
2.78  1012
2.56  1012
a2 (cm W1)

7.76  106
1.15  105

Z-scans could result from a different process, which is 2PA along

with ESA for the fs pulsed laser and 2PA alone for the CW laser.
By fitting the closed aperture Z-scan data with eqn (A.7) and
(A.8), the non-linear refractive index coefficient (n2) is extracted
and the related real part of third-order susceptibility <(w(3)(o;
a0 (m1)

o, o, o)) are calculated. The impact of pulsed and CW mode

2.80
2.60

2.56
4.02

illumination on the non-linear behavior is outlined from the

comparison of the CA Z-scan results. The valley before peak
Compound

configuration arises as a result of fs-pulsed laser being a light

3A25D2
3A25D4

3A25D2
3A25D4

source, which demonstrates the presence of a self-focusing effect

consequently to a positive non-linearity (n2 4 0). Under CW laser
excitation, the experimental results are completely opposite to
those of the pulsed laser mode, which is the configuration of
fs pulsed laser,

a peak followed by a valley, expressing a self-defocusing

CW laser,

effect indicator to a negative non-linearity (n2 o 0). The physical

800 nm

532 nm
Table 6

Laser

origins that contribute to the non-linear refraction include elec-

tronic polarization, molecular reorientation, electrostriction, and

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Paper
thermal effects.27 The thermal and electronic non-linearities
possess same effects in Z-scan measurement; however, their
underlying physical mechanisms are different. In electronic
polarization, the optical field distorts the electron cloud around
an atom or molecule, triggering the non-linear electronic polar-
ization of the medium, in turn modifying the refractive index,
which is known as the optical Kerr effect. The refractive index of a
material depends on the intensity of the optical beam (n = n0 +
n2I). In the thermal effects, the laser energy that passes through
the medium is absorbed, resulting in the formation of a diverging
thermal lens within the sample and a variation of refractive index
 
dn
with temperature n ¼ n0 þ T . A phase shift (Df0) in the
dT
laser beam is generated by the thermal lens, hence resulting in a
diffraction ring pattern when Df0 4 2p radians and a self-
defocusing effect when Df0 o 2p radians.74 This explains the
occurrence of the phenomenon of self-defocusing under a CW
laser. The heating of the medium caused by the CW laser is more
than the heating caused by the fs pulsed laser. Consequently, the
effect of thermal non-linearity is more considerable in the CW
laser domain than in the fs pulsed laser. Besides, the peak-valley
differences (DZpv) of the CA Z-scan traces can also identify the
origin of non-linearity, DZpv is 1.7 times ZR in the case of purely
Kerr effect, while it is larger than 1.7ZR in the case of the thermal
lens effect.75 The DZpv of the CA transmittance data are found in
nearly 1.7ZR with an fs pulsed laser mode, suggesting that the
larger electronic contribution to NLR is observed. The extremely
weak thermal lens in the fs pulsed laser domain is a consequence
of the low laser repetition rate, i.e., 1 kHz. The CA Z-scan curve of
3A25D2 and 3A25D4 shows a DZpv 4.4 and 3.5 times the ZR as the
CW laser is used, which agrees with the finding of self-defocusing
characteristic and lends support to the non-linear effect that is
predominantly thermal in origin. The thermal-optical coefficient
(dn/dT) is the change in the thermally induced non-linear
refractive index coefficient against temperature. For the steady-
state case, it can be calculated from the n2 value achieved from
the CW Z-scan trace using the expression.76–78
      Tsuboya et al. studied the quadratic hyperpolarizability of
dn Ia0 t dn a0 o02
n2 ¼ ¼ (2)
dT rc dT 4k
where I is the incident intensity, r is the density, c is the specific
heat capacity, t (= o02rc/4k) is the thermal relaxation time, and k
is the thermal conductivity of the solvent. The k value of DMF is
0.184 W m1 K1 at room temperature. 3A25D2 and 3A25D4
exhibit a negative thermal lens, and their dn/dT are found to be
3.64  105 and 1.57  104 K1, respectively. The accumula-
tion of thermal effects with CW excitation leads to the values of n2
and w(3)(o; o, o, o) that are extremely high as compared to
that with pulsed excitation.
The estimated values of a2, n2, and w(3)(o; o, o, o) are
found to be of the order of 1012 cm W1, 1017 cm2 W1, and
1015 esu at the fs pulsed laser mode and 105 cm W1,
109 cm2 W1, and 107 esu at the CW laser mode (Table 6).
The measured values are comparable to some chalcone deriva-
tives reported. Under the fs Z-scan method, the a2 of 3A25D2
and 3A25D4 are within the same order of magnitude with the
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Fig. 15 Optical limiting of 3A25D2 (green) and 3A25D4 (magenta) with
femtosecond pulsed laser domain. Symbols represent the experimental
data while the dotted lines are the theoretical fits.
4 0 -fluoro-3,4,5-trimethoxychlocone (3TF) and 4 0 -chloro-3,4,5-
trimethoxychlocone (3TC)79 (130 fs and 780 nm laser pulses)
and three bis-chalcone substituted with methoxy (V1), methyl-
sulfanyl (V2), and dimethylamino (V3) groups80 (170 fs and
800 nm laser pulses). However, the n2 and w(3) of 3A25D2 and
3A25D4 are one order of magnitude smaller than those reported
for the chalcone derivatives. 3A25D2 and 3A25D4 have the same
order of magnitude of the CW laser NLO parameters with 2,3,4-
trimethoxy-4 0 -nitrochalcone (2,3,4TMNC),81 4-bromothiophenyl
chalcone (2AT4B),82 and 4,5 0 -dibromothiophenyl chalcone
(B5B2SC).83 To appraise the contribution of third-order optical
non-linearity per molecule, the molecular non-linear property is
defined as the cubic hyperpolarizability (g), which is related to
the third-order susceptibility and given by eqn (A.1). The g(o;
o, o, o) is determined in B1034 and B1026 esu in fs pulsed
and CW domain, respectively. The experimental results at fs
pulsed laser with 800 nm wavelength are comparable to our
theoretical studies (see Section 3.6.5).
para-, meta-, and ortho-carborane-ferrocene-conjugated dyads,
and found that the para-carborane dyad exhibits relatively higher
NLO response than ortho- and meta-carborane analogues84 due to
its longer effective conjugation length.2 Therefore, we predict that
higher NLO properties will be determined for 3A25D2 in our
study due to its para-substituted chlorine. From Table 6, it is
worth noting that 3A25D2 shows a stronger non-linearity than
3A25D4 in the fs pulsed regime, which corroborates our postulate
and the theoretical studies (see Section 3.6.5). Even though the
inverse relationship is found in the CW laser domain, the a2 and
n2 of 3A25D4 are much larger than that of 3A25D2. The opposite
results in CW laser Z-scan might be attributed to the different
thermal diffusivity of both the compounds; 3A25D4 becomes
hotter than 3A25D2 after absorbing the energy of the laser. The
thermal lens effect is dependent on temperature, denoting that
the hotter compound will have higher non-linear refraction; thus,
the third-order NLO susceptibility of 3A25D4 is approximately 6
times that of 3A25D2 in the CW domain.
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3.6.2. Optical limiting and figures of merit for all-optical
switching. A material’s non-linear response is useful in the
application of optical limiting due to its ability to block the
penetration of high-irradiance light, thus restricting the output
laser to safe levels. The materials displaying strong 2PA and
NLR properties with a low limiting threshold, a larger dynamic
range, and a broad spectral response, have great potential for
limiting devices. Considering that a2 and n2 are irradiance-
dependent, short input pulse operation promotes the limiting
response.85 Here, we measured the optical limiting performance
of 3A25D2 and 3A25D4 in DMF solution with an increasing
incident energy of an fs pulsed laser at 800 nm wavelength.
Fig. 15 shows the normalized transmittance of both the solutions
against the input laser fluences and fitting with the equation.
 
pffiffiffiffiffiffiffiffi Ein
FðzÞ ¼ 4 ln 2 3=2 oðzÞ2 (3)
p
where F(z) is the input laser fluence, Ein is the laser energy, and
o(z) is the beam radius at a given z-position along the beam,
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
which is given by oðzÞ ¼ o0 1 þ ðz=z0 Þ2 . The threshold fluence
for optical limiting is determined at the point where the input
fluence falls to 50% of the linear transmittance, viz., 2.20 and
2.16 mJ cm2 for 3A25D2 and 3A25D4, respectively. Because of
their strong ESA and MPA processes, the title compounds have a
lower optical limiting threshold than previously examined com-
pounds; thus, these compounds are accountable for the limiting
devices.
A non-linear material that can be used for all-optical switching
in waveguides can define by figures of merit concerning a2 and n2.
Two limits are needed for switching, which is one-photon FOM:
W = (n2I0)/(a0l) 4 1 and two-photon FOM: T = (a2l)/(n2) o 1. The W
is observed to be more than unity with fs pulsed and CW inputs
due to the strong non-linear refraction of 3A25D2 and 3A25D4. The
T are o1 in the CW domain but 41 in the fs pulsed domain;
hence, the title compounds are only used successfully for all-
optical switching devices with CW inputs.
3.7. Theoretical studies of molecules at distinct environments
3.7.1. Structure deformation induced by distinct environ-
ments. In order to study the electronic and optical properties
distinctions in the structures of 3A25D2 and 3A25D4, a DFT
computational study was performed to optimize the structures
Fig. 16 Overlay diagram of vacuum (green), liquid (red), and crystalline (blue) optimized geometries of (a) 3A25D2 and (b) 3A25D4 molecules at the
B3LYP/6-311++G(d,p) level of theory. The C1–C4–C5–C6 (t1), O1QC5–C6QC7(t2), and C6QC7–C8–C9 (t3) torsion angles are listed with respective
colors.
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in vacuum, solvent (DMF solution), and crystalline (CHELPG
scheme) environments. The graph of bond length and bond
angle variation for each optimized geometry is plotted in
Fig. S10 (ESI†), showing that each geometry along with the
HAR-refined structure have quite close bond lengths and
dihedral angles. However, the considerable deviation of
C1–C4–C5–C6 (t1), O1QC5–C6QC7(t2), and C6QC7–C8–C9
(t3) torsion angles indicates that the optimized geometries
are twisted to each other, as seen in Fig. 16. In the vacuum
and liquid, 3A25D2 is deformed to a bending structure, while
the thienyl and phenyl rings of 3A25D4 are inclined to the
enone group in an opposite direction relative to the crystalline
structure. The single point energy of distinct environments
optimized structures is calculated and given in Table S3 (ESI†),
implying that the crystalline optimized structures have the
highest energy. Besides, the computation environments lead
to changes in bond length alternation (BLA), which is defined
as the difference between the average lengths of the single and
double bonds along the linear p-conjugated backbone.86–88 BLA
is a good predictor of linear and non-linear optical properties.
BLA = rC6QC7  (rC5–C6 + rC7–C8)/2 is determined (Table S4, ESI†)
and the highest (less negative) BLA are found in the liquid
among the computational environment, which in turn predicts
that both the molecules exhibit the highest NLO properties in
the liquid.
3.7.2. Frontier molecular orbitals. The energy of the high-
est occupied molecular orbital (HOMO), the lowest unoccupied
molecular orbital (LUMO), and energy gap could replicate the
structure’s chemical activity, which affects its electrical and
optical characteristics, which motivates us to perform TD-DFT
calculations to determine the HOMO–LUMO gap.89 Fig. 17 shows
the energy level map of the 11 highest occupied and 11 lowest
unoccupied molecular orbitals at different states, and also the
HOMO–LUMO gap. Hirshfeld weighting function is used for
decomposing the orbital to the fragment composition,90 namely,
enone bridge, dichlorothienyl (Cl2-Th), and dichlorophenyl (Cl2-
Ph) rings. Each energy level in Fig. 17 is divided into three colors,
which are contributed by the corresponding fragment composi-
tions. The HOMO and LUMO maps are also depicted in Fig. 17
along with the corresponding orbital delocalization index (ODI).
P 2
The ODI is expressed as ODIi ¼ 0:01  YA;i , where YA,i is
A
the composition of atom A in orbital i.91 The stronger degree of
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Fig. 17 HOMOs (where blue and green represent positive and negative phase, respectively) and LUMOs (where red and yellow represent positive and
negative phase, respectively) of 3A25D2 and 3A25D4 calculated in vacuum, solvent (DMF solution), and crystalline (CHELPG scheme) phases, along with
the corresponding energy level (color blocks), orbital delocalization index (magenta texts), and HOMO–LUMO energy gap (EH-L) (dark arrow).
orbital delocalization (localization) is indicated by the lower
(higher) ODI. The HOMOs present p-bond located in the thienyl
rings and the LUMOs present p-bond conjugated in the enone
bridge and partially in the phenyl rings, signifying their electron-
donating and accepting abilities, respectively. It is clearly
observed that the HOMOs are found to be of the highest energy
in liquid and possess stronger orbital localization (higher ODI).
The LUMOs are found in a contrary manner, which shifts to a
lower energy in the liquid with stronger orbital delocalization
(lower ODI). Thereby, the HOMO–LUMO energy gaps in the
liquid (EH–L = 2.65 eV for 3A25D2 and EH–L = 2.89 eV for
3A25D4) are smaller than that in the vacuum and crystalline
phases (EH–L = 3.90/3.97 eV for 3A25D2 and EH–L = 4.02/4.09 eV for
3A25D4), as a noteworthy result to the solvent effect of high polar
DMF solution. It is worth mentioning that the lower the EH–L, the
better the non-linear optical property of the medium. Based on
the EH–L values, we can know that the molecules may have the
highest (hyper)polarizability in liquid. Besides, the small varia-
tion in EH–L in the vacuum and crystalline phases demonstrate
that these CHELPG schemes marginally affect their individual
HOMO and LUMO energies. The HOMO–LUMO energy gap of
3A25D2 is evidently smaller than that of 3A25D4 in all the three
computing phases environments, implying that it has higher
reactivity and optical polarizability. In addition, the weight of the
phenyl ring in the HOMO for 3A25D2 is significantly larger than
that for 3A25D4, suggesting that the substitution position on the
phenyl ring could affect the electron-donating ability.
3.7.3. Aromaticity and electron delocalization. Aromaticity
and p-conjugation topology can act as fundamental terms to
dictate the linear and non-linear optical properties. The decrease
in the aromaticity is accompanied by the decrease in the HOMO–
LUMO gap, which in turn affects a bathochromic shift in the UV
spectra and an increase in the NLO properties. The aromaticity
can be defined by many criteria based on magnetic, geometry,
and electron delocalization. In our study, 3A25D2 and 3A25D4
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Table 7 The aromaticity index of 3A25D2 and 3A25D4 molecules, viz.,
multicenter bond order (MCBO), para-delocalization index (PDI), and electron
localization function-p (ELF-p) calculated in three distinct environments
MCBO PDI ELF-p
3A25D2 0.0608 0.0831 0.8330
3A25D4 0.0625 0.0857 0.8507
molecules consist of a Cl4 atom each attached at different
positions of the phenyl ring, which in turn slightly influences
its aromaticity. We elucidated the aromaticity of both the
compounds, such as multicenter bond order (MCBO), para-
delocalization index (PDI), and electron localization function-p
(ELF-p). These molecular structures are optimized without the
diffusion function in a vacuum. The aromaticity indices are listed
in Table 7. MCBO is known better as the two-center Mayer bond
order, which determines the degree of conjugation.92 PDI is
essentially the averaged delocalization index of para-related
carbon atoms in a six-membered ring.93 The larger aromaticity
of the 3A25D4’s phenyl ring is indicated by its larger MCBO and
PDI values compared to that of 3A25D2. ELF-p is an electron
localization function that solely contributed to p-electrons, which
well reveals the delocalization of p-electrons in the molecules.94
Due to the optimized title molecules being non-planar, the ELF-p
are calculated based on the p type localized molecular orbitals
(LMOs). The molecule possesses the p aromaticity characteristic
if ELF-p is larger than 0.70. The isosurfaces of ELF-p (isovalue =
0.70) along with the bifurcation points, which are defined in the
topology analysis framework, are shown in Fig. 18. The bifurca-
tion points of ELF-p correspond to the positions where an ELF-p
domain begins to divide into two with the isovalue increasing. If
the ELF-p value at the bifurcation point is larger, it demonstrates
that the electron has more degree to delocalize between the two
split ELF-p domains. The quasi-doughnut-shaped ELF-p domains
of the phenyl rings are connected with a high bifurcation value
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Fig. 18 ELF-p isosurfaces (vacuum phase) of (a) 3A25D2 and (b) 3A25D4 molecules with an isovalue of 0.70. The orange spheres highlight the positions
of the bifurcation points, and the black text indicates the exact ELF-p value at these points.
ranging from 0.83 for 3A25D2 to 0.85 for 3A25D4. The slightly
larger ELF-p index for 3A25D4 exhibits that its phenyl ring has a
higher aromaticity than that of 3A25D2 under the influences of
the position of the chlorine substituents. The disconnecting of
ELF-p domains and the low ELF-p index are found on the thienyl
ring and the enone bridge, indicating that the electron is difficult
to be delocalized over the whole molecule, and hence reduced its
non-linearity.
3.7.4. Electronic absorption spectra. The first 20 excited
states of the title molecules are calculated in three environ-
ments, i.e., vacuum, liquid (DMF solution), and crystalline
(CHELPG scheme) using the TD-DFT method. The electronic
absorption spectra are simulated by Gaussian broadening
function with full width at half maximum (FWHM) of 0.667 eV
and recorded in the range of UV-Vis-NIR, as shown in Fig. 19. The
ghost-hunter analysis is carried out to omit the ghost excited states
that resulted from the erroneous asymptotic behavior of the
exchange potential of the low Hartree–Fock exchange composition
hybrid functional.95 The UV spectra of the title molecules consists
of two major absorption maxima, namely, band I (prominent band
located in 290–340 nm region) and band II (relatively minor band
situated in 220–260 nm region). As seen in the spectra, the solvent
effect of the DMF solution causes an abrupt absorption shift, band
I is 17–22 nm blue-shifted, while band II is blue-shifted for 3A25D2
and red-shifted for 3A25D4. The solvent effect also causes an
increase in the band I absorption intensity and a decrease in the
band II absorption intensity. The closer results in vacuum and
crystalline phases indicate that the CHELPG scheme only margin-
ally affects the electronic properties. The band I in the liquid are in
close agreement with the experimental absorption peaks (Fig. 11)
at 319 and 298 nm for 3A25D2 and 3A25D4, respectively. Band I for
3A25D2 is slightly red-shifted compared to 3A25D4, meaning that
3A25D2 requires less energy for electronic transition, which is
consistent with the result of its smaller HOMO–LUMO energy gap.
The electronic transition attributed to the absorption bands
is shown as discrete spikes below the spectra. The electronic
transitions attributed to the band I are found in the same
excitations in vacuum and crystalline environments, which are
S0 - S3 and S0 - S4 excitations for 3A25D2 and 3A25D4,
respectively, mainly assigned to the electronic transition
HOMO1 - LUMO. The band I in liquid originates from doubly
degenerate S0 - S5 and S0 - S6 excitations for 3A25D2 corres-
ponding to HOMO3 - LUMO (10%/5%), HOMO2 - LUMO
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(52%/26%), and HOMO - LUMO+2 (35%/62%), whereas it is
attributed to S0 - S6 and S0 - S7 excitation for 3A25D4 from the
electronic transition from HOMO4 (65%/26%), HOMO3 (16%/
26%), and HOMO2 (8%/37%) to LUMO. Band II corresponds to
the S0 - S6 and S0 - S8 excitations in vacuum and crystalline
environments for 3A25D2. S0 - S15 and S0 - S16 excitations
contributed to band II for 3A25D2 in liquid. The band II for
3A25D4 is mainly made up of the multiply degenerate excitations,
viz., S0 - S6, S0 - S16, and S0 - S18 (vacuum), S0 - S15 and
S0 - S20 (liquid), S0 - S6, S0 - S9, and S0 - S14 (crystalline).
The oscillator strength of S0 - S6 in vacuum and crystalline
environments are relatively higher than other excitations under
band II, hence leading to a hyperchromic shift. All electronic
transitions with their primary contributions to the UV-Vis
spectrum are listed in Table 8, along with their corresponding
excitation energies, excitation wavelength, oscillator strength,
and orbital contributions.
The hole–electron analysis96 is conducted to determine the
charge transfer path of excitation.97,98 During the electronic
transition, the electrons leave ‘‘holes’’ and go to ‘‘electrons’’.
Fig. 20 and 21 show the hole–electron distribution isosurface of
the excitations listed in Table 8; holes and electrons are
displayed in grey and yellow isosurfaces, respectively. Besides,
the amount of charge transfer between various fragments in the
electron excitation process is evaluated by the inter-fragment
charge transfer (IFCT) method. The heat map of the charge
transfer matrix is a data visualization technique that shows the
condition of charge transfer, and the charge-transfer spectrum
graphically presented the contribution of the electron transfer
component and the redistribution component to the UV-Vis
spectrum. The heat maps of charge transfer are generated in
Fig. S11 and S12 (ESI†), and the charge-transfer spectrum are
incorporated with the simulated absorption spectrum in
Fig. 19. During the excitations assigned to band I, the electrons
are found to be highly originated from the cinnamoyl system
(leaves the p-orbitals on the phenyl ring and goes to the
p*-orbitals on the enone group), except for 3A25D2 in the
liquid, S0 - S5 excitation is resulted from the p–p* transition
throughout the overall molecule and the S0 - S6 excitation is
ascribed to p–p* transition from the thienyl ring to the cinna-
moyl system. From the charge-transfer spectrum, the band II
for 3A25D2 are involved in the mixed character of p–p* and
n–p* transitions, but the major contribution is the electron
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Fig. 19 Electronic absorption spectra (black) of molecules 3A25D2 (left) and 3A25D4 (right) at vacuum (top), solvent (middle), and crystalline (below)
environments. The charge-transfer spectrum is shown in the color lines and plotted with zoom-in (inset graphs). The peak positions of the absorption
bands (lmax) are labelled in blue text. The oscillator strength of the selected excitation transitions (major contribution for absorption bands) is shown as
distinct spikes and labelled in red text.

redistribution within the thienyl ring. The band II for 3A25D4 (vacuum), charge transfer from the thienyl ring to the phenyl
also shows mixed charge-transfer character but with different ring (liquid), and redistribution within thienyl (crystalline).
major contributions, i.e., redistribution within the phenyl ring From the hole–electron distribution maps, we can conclude

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Table 8 The excitation energy (Eex, in eV), absorption wavelength (lex, in nm), oscillator strength (fo), and contribution of FMOs (in %) for 3A25D2 and
3A25D4 compounds on different excited transitions (S0 - Sn)

Environments S0 - Sn Eex lex fo mtran Major contribution (410%)

3A25D2
Vacuum S0 - S3 3.7110 334 0.5684 6.35 H1 - L (79%), H - L (10%)
S0 - S6 4.7323 262 0.2028 3.36 H - L+1 (84%)
S0 - S8 4.9514 250 0.0716 1.95 H - L+2 (37%), H2 - L+1 (23%), H1 - L+2 (19%)
Solvent S0 - S5 3.9041 318 0.3536 4.89 H3 - L (10%), H2 - L (52%), H - L+2 (35%)
S0 - S6 4.0115 309 0.3350 4.69 H2 - L (26%), H - L+2 (62%)
S0 - S15 4.9729 249 0.1000 2.30 H6 - L (17%), H2 - L+1 (54%), H1 - L+2 (14%)
S0 - S16 5.0103 247 0.1079 2.38 H - L + 5 (59%)
Crystalline S0 - S3 3.7765 328 0.4577 5.65 H1 - L (88%)
S0 - S6 4.8421 256 0.2379 3.60 H - L+1 (90%)
S0 - S8 5.0840 244 0.0863 2.12 H - L+2 (43%), H1 - L+2 (20%), H1 - L+1 (17%), H3 - L+1 (12%)
3A25D4
Vacuum S0 - S4 3.9319 315 0.3626 4.93 H1 - L (82%)
S0 - S6 4.8442 256 0.1448 2.81 H - L+1 (95%)
S0 - S16 5.4821 226 0.1073 2.27 H2 - L+1 (48%), H1 - L+2 (30%)
S0 - S18 5.6072 221 0.1136 2.31 H2 - L+2 (52%), H1 - L+3 (14%)
Solvent S0 - S6 4.1111 302 0.0710 2.13 H4 - L (65%), H3 - L (16%)
S0 - S7 4.1881 296 0.3448 4.66 H4 - L (26%), H3 - L (26%), H2 - L (37%)
S0 - S15 5.0833 244 0.1208 2.50 H1 - L+2 (16%), H - L+5 (68%)
S0 - S20 5.3273 233 0.1017 2.24 H8 - L (26%), H2 - L+2 (61%)
Crystalline S0 - S4 3.9472 314 0.3023 4.49 H2 - L (22%), H1 - L (66%)
S0 - S6 4.9750 249 0.1471 2.79 H - L+1 (95%)
S0 - S9 5.2393 236 0.0756 1.95 H5 - LUMO (17%), H1 - L+1 (66%)
S0 - S14 5.4949 226 0.0793 1.95 H6 - LUMO (88%)

Fig. 20 Hole–electron distribution maps of main excitations that contributed to bands I and II for 3A25D2 at three environments. Grey and yellow
isosurfaces represent the hole and electron distributions, respectively. The blue arrow represents the transition dipole moment vector.

that the solvent effect changes the characteristics of the excited
states significantly, especially for the excitations contributing
to band II.
3.7.5. Non-linear optical properties. The molecular non-
linearity of 3A25D2 and 3A25D4 molecules in the frequency-
dependent field (l = 532, 637, 655, 800, 1064, 1200, 1310, and
1600 nm) and the zero-frequency limit (l = N nm, which is set
as 999 999 nm of the incident wavelength in the Gaussian 09
software) computed at different environments are listed in Tables
S5–S11 (ESI†). The computational results reveal that 3A25D2
possesses larger (hyper)polarizabilities relative to 3A25D4. It
indeed supports the postulate made in Section 3.7.3 that the
system with low aromaticity and narrowed HOMO–LUMO energy
gap potentially shows higher strength of non-linear optical
properties. The formula of isotropic average polarizability hai,
anisotropic polarizability Da, projection of quadratic hyper-
polarizability on dipole moment bvec, and the average of cubic
hyperpolarizability hgi are expressed in the Appendix A.2.
The total dipole moment at three distinct environments is
found in the range of 2.96–5.23 Debye. We further analyzed the
fragment dipole moment based on the Hirshfeld weighting
function to clarify the characteristic of their polarity. The
optimized structures are partitioned into fragments, viz., enone
bridge, dichlorothienyl, and dichlorophenyl rings. Fig. 22 presents

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Fig. 21 Hole–electron distribution maps of main excitations that contributed to bands I and II for 3A25D4 at three environments. Grey and yellow
isosurfaces represent the hole and electron distributions, respectively. The blue arrow represents the transition dipole moment vector.

Fig. 22 The optimized 3A25D2 (top) and 3A25D4 (below) molecules in (a) vacuum, (b) solvent, and (c) crystalline environments with the fragment dipole
moment (m) vector that contribute to the dichlorothienyl ring (green arrow), enone moieties (red arrow), and dichlorophenyl ring (blue arrow). The longer
arrow represents a larger m.

the fragment dipole moment vector that is directed toward the

positive charge part. The direction and magnitude of the fragment
dipole moment are nearly identical in vacuum and liquid environ-
ments, whereas all the vectors in the crystalline point in different
directions with a larger magnitude of the fragment dipole
moments. This could be due to the induction effect of the crystal-
line environment polarization. However, the vector of the dipole
moment of the enone moieties are opposite to that of the aromatic
rings at both the ends of molecules; thus, the dipoles are cancelled
out and result in a reduced total dipole moment for the crystalline
environment compared to liquid environments. The induced
dipole moment is related to the (hyper)polarizabilities; therefore,
the (hyper)polarizabilities in the crystalline environment are less
than that of the liquid.
The trend of frequency-dependent (hyper)polarizability in
various environments is clearly depicted by the graph of the 3D
trajectory (Fig. 23–25). Generally, the (hyper)polarizabilities in
various environments decrease with the increase in the external Fig. 23 Isotropic average static polarizabilities hai(0; 0) and dynamic polariz-
field wavelength and exhibit convergence at the zero-frequency abilities hai(o; o) in vacuum (V), solvent (S), and crystalline (C) environments.

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Fig. 24 The projection of quadratic hyperpolarizability on dipole moment (bvec) associated with the functions of (a) electro-optic Pockels effect (EOPE)
b(o; o, 0) and (b) second harmonic generation (SHG) b(2o; o, o) along with static quadratic hyperpolarizability b(0; 0, 0) in vacuum (V), solvent (S), and
crystalline (C) environments. Some of the bvec(2o; o, o) values are negative (Tables S8 and S9, ESI†) due to the deviation of the total hyperpolarizability
away from the dipole moment. The negative signs are omitted in the graph for clarity.

limit, which is close to the static values in vacuum and crystal-
line environments. The convergence value and static value
show a significant discrepancy in the solution. A comparable
situation has been reported by Hua et al.99 Fig. 23 shows the
lower slopes of hai(o; o) against the wavelength, implying
the weak relationship between the dynamic polarizability and
the external field. The polarizability of 3A25D2 and 3A25D4
molecules is influenced by the calculated environment; the
order of hai is solvent 4 vacuum 4 crystalline.
The strong optical resonance effect is shown in quadratic
and cubic hyperpolarizabilities. The electro-optic Pockels effect
(EOPE) b(o; o, 0) and dc-Kerr g(o; o, 0, 0) concave decrease
with the increase in the electric field wavelength (Fig. 24a
and 25a). The hyperpolarizabilities in the DMF solution are
markedly higher than the values in vacuum and crystalline
environments, showing that the non-linearity is enhanced
due to the solvent polarity and weakened by the crystalline
environment polarization. The NLO properties of a conjugated
molecule could be induced by the changes in the BLA para-
meters in different environments. Fig. 24b and 25b illustrate
the hyperpolarizabilities related to the second harmonic
generation, i.e., b(2o; o, o) and g(2o; o, o, 0). Anomalous
outliers appear at wavelengths of 637 and 655 nm. It proved the
two-state model, which expects high NLO responses when the
incident light is twice the maximum absorption wavelength of
the molecules.
In order to compare the cubic NLO properties for Z-scan
experiment, we have evaluated the value of intensity-dependent
refractive index (IDRI) g(o; o, o, o) and third harmonic
generation g(3o; o, o, o) from dc-Kerr g(o; o, 0, 0) and
static g (Table S12, ESI†). Following previous work,100,101 the
average hyperpolarizabilities are derived for small frequencies
as follows.
hg(o; o, o, o)i D 2hg(o; o, 0, 0)i  hg(0; 0, 0, 0)i (4)
hg(3o; o, o, o)i D 6hg(o; o, 0, 0)i  5hg(0; 0, 0, 0)i (5)
The changing trends of g(o; o, o, o) and g(3o; o, o, o) are
consistent with the g(o; o, 0, 0) variable but are more obvious due
to the non-proportional relationships. The considerable solvent
effect on the cubic hyperpolarizabilities of the 3A25D2 and 3A25D4
molecules implies that the NLO properties of the molecules can be
varied by altering the environment. The g(o; o, o, o) of 3A25D2
and 3A25D4 molecules in DMF solution is 18.41  1034 and
8.97  1034 esu at 532 nm wavelength and 4.69  1034 and
2.68  1034 esu at 800 nm wavelength. The DFT computed values
for g(o; o, o, o) are consistent with the experimental values by
fs pulse Z-scan at 800 nm wavelength (both are of the order of
1034) but approximately 107 times smaller than the values
obtained by CW Z-scan at 532 nm wavelength. This difference
reflects that the non-linearity in the CW-laser Z-scan experiment is
predominately thermal in origin.
The Lorentz–Lorenz relation expresses the linear refractive
index of a solid material in terms of the atomic polarizability
(SI units) as follows.
n02  1 N hai rNA Z
¼ ¼ hai ¼ hai (6)
n02 þ 2 3e0 3e0 M 3e0 Vuc
where N is the number density of molecules (N = rNA/M = Z/
Vuc), r is the density of the crystal, NA is Avogadro’s constant, e0

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Fig. 25 Average of cubic hyperpolarizability hgi associated with the functions of (a) electro-optic Kerr effect (dc-Kerr) g(o; o, 0, 0), (b) electric field
second harmonic generation (EFISHG) g(2o; o, o, 0), (c) third-harmonic generation (THG) g(3o; o, o, o), and (d) intensity-dependent refractive index
(IDRI) g(o; o, o, o), along with static cubic hyperpolarizability g(0; 0, 0, 0) in vacuum (V), solvent (S), and crystalline (C) environments.

is the permittivity of free space, M is the molar mass, Z is the predict the n0 and w(3) of the title molecules in the crystal form
number of formula entities per unit cell, and Vuc is the volume by substitution with the values of ha(0)i and hg(o; o, o, o)i
of unit cell. r, Z, and Vuc are obtained through crystallographic calculated in a crystalline environment. The calculated w(3)
results (Table 4). The third-order NLO susceptibility w(3) of the value approach the result of the reported crystal BRC.7 (Table 9)
crystal can be determined by the relation with the number
density of crystal and its cubic hyperpolarizability (SI unit) as
follows.
Table 9 The third-order optical nonlinearity of 3A25D2 and 3A25D4 in a
ð3Þ L4 N hgi crystalline environment (esu)
w ¼ (7)
e0
ha(0)i n0 hg(o; o, o, o)i w(3)(o; o, o, o)
4 2
where L is the Lorentz local field factor (L = (n0 + 2)/3) (see 3A25D2 3.67  1023 1.86 2.12  1034 7.61  105
eqn (5.2.3a) and (5.2.4a) of Boyd102). The equations allow to 3A25D4 3.46  1023 1.79 1.15  1034 3.47  105

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Table 10 The static cubic hyperpolarizability is estimated by numerical

integration (NI) and by the analytical derivative method (AD) (1034 esu)

3A25D2 3A25D4
Static g NI AD NI AD
gxxxx 4.39 4.09 2.65 2.48
gyyyy 0.19 0.18 0.21 0.22
gzzzz 0.12 0.12 0.12 0.12

We have further investigated the spatial distributions of the

cubic hyperpolarizability density and the decomposition of the
cubic hyperpolarizability contribution by numerical integration
in order to understand the characteristic of non-linearity.103–105
The vacuum phase optimized structures are utilized in the DFT
calculations with an electric field applied along each Cartesian
axis. The cubic hyperpolarizability density diagonal tensor
- (3) - (3) -
[r(3)
xxx(r ), ryyy(r ) and rzzz(r )] are determined via finite difference
method (see Appendix A.3). The integrand function of r(3) iii (r) is
(3) -
iriii (r) [i = x, y, z], which is defined as the local contribution
to the static giiii. The numerical integration of the ir(3)
function agrees well with the static giiii obtained by the CPKS
method (Table 10), showing the validity of the hyperpolarizability
-
density analyses. Fig. 26 shows that the isosurfaces of ir(3) iii (r) for
3A25D2 and 3A25D4 molecules with an isovalue of 200.0 a.u.,
where red and blue isosurfaces represent the positive and nega-
tive local contributions, respectively. The x-component is respon-
sible for a substantial portion of the local contribution function,
followed by the y-component, and then the z-component, which
is consistent with the results of gxxxx 4 gyyyy 4 gzzzz.
The hyperpolarizability decomposition analysis is useful in
explaining the effect of the substitution position on NLO
response.106 The contribution of molecular fragments to giiii
-
is measured by integration to the ir(3) iii (r) function, where all
the atoms are based on the Becke atomic space.107 Fig. 27
illustrates the decomposed giiii values of each fragment, e.g.,
enone bridge (En), thienyl ring (Th), phenyl ring (Ph), and four
Cl substitutions (Cl1–Cl4, labels see Fig. 2). The contribution of
En is low in each cartesian axis with a negative contribution in
the x-axis and positive contribution in the y- and z-axes, while
Fig. 27 Decomposition of the cubic hyperpolarizability components into
each fragment by integrating the local contributions of ir(3)
-
- iii (r ). En: enone
bridge, Th: thienyl ring, and Ph: phenyl ring.
-
iii (r)
for other fragments, the x-component of g is much larger than
that of the y- and z-components. The contribution of each
fragment is nearly equal for both molecules, except for the unit
of Cl4. The Cl4 in 3A25D2 contributes a considerably larger
x-component of g relative to that for 3A25D4, while the
y-component is slightly lower from 3A25D2 to 3A25D4. This
observation could because the gxxxx of 3A25D2 is 2-fold larger
than that of 3A25D4 and the approximate gyyyy values among
them. It shows the importance of para-substitution rather than
ortho-substitution on cubic hyperpolarizability, and conse-
quently affords the higher third-order NLO response than
3A25D4. Thus, the substitution at the para-position of the
phenyl ring is preferred on the designed high-performance
chalcones for NLO application.
4. Conclusion
Two thienyl chalcones (3A25D2 and 3A25D4) are synthesized
and characterized through FT-IR, NMR analyses, as well as

-
Fig. 26 Diagrams of the local contribution functions of cubic hyperpolarizabilities tensor ir(3)
iii (r ) of 3A25D2 (top) and 3A25D4 (bottom) molecules
(isovalue = 200.0 a.u.).

This journal is © the Owner Societies 2022 Phys. Chem. Chem. Phys., 2022, 24, 21927–21953 | 21947
Paper PCCP

structural determination by the SCXRD method. The consider- Appendix A

able variation of crystal packing, charge distribution, photophy- A.1 Equations of Z-scan measurements
sical, and NLO properties among two compounds with chlorine
atom (Cl4) attached at the para- or ortho-position of the phenyl In order to extract the non-linear absorption coefficient (a2) (in
ring are comprehensively studied. The effect of the media (e.g., cm W1), the normalized OA curves are fitted by ref. 108.
vacuum, solvent, and crystalline) on the optical and electronic
a2 I0 Leff
properties of the two molecules are studied theoretically using TOA ¼ 1  "  # (A.1)
the (TD)-DFT method. The absorption spectra of the two mole-
pffiffiffi z 2
2 2 þ1
cules calculated with the solvent model correlate well with those zR
observed in the experiment. The solvent effect induced by the
high-polarity of the DMF solvent results in a considerable blue- where TOA is the normalized transmittance for OA Z-scan,
shift of the electronic absorption spectra in the solution com- I0 = 2P/po02 is the on-axis irradiance at focus in W cm2, z is
pared with that in vacuum and crystalline environments. On the the distance of the sample from the focus, Leff is the effective
contrary, the CHELPG scheme of the crystalline environment length of the sample, and zR is the Rayleigh range, which is
leads to a weak absorption shift when compared to the vacuum. given by the following equations.
Electronic transition analysis revealed the influence of the med-
ium and substitutional position of Cl4 on the intramolecular 1 
Leff ¼ 1  ea0 l (A.2)
charge transfer process. The induced strengthening effect on the a0
response properties of solvation and weakening effect owing to
the CHELPG scheme (crystalline) to the system was revealed by
the overwhelming (hyper)polarizabilities in the liquid relative to po02
zR ¼ (A.3)
the vacuum and crystalline environments. The cubic hyperpolar- l
izability (g) of theoretical and experimental Z-scan with fs pulsed
laser (800 nm) are of the order of 1034 but extremely different where a0 is the linear absorption coefficient of the sample in
with the data in the CW domain (532 nm) due to the high cm1, l is the sample length, o0 is the beam waist radius at the
accumulation of the thermal effect contribution toward the focus, and l is the wavelength of the laser.
experimental non-linear refraction. The role of each moiety of The absorption cross-section of two-photon absorption (s2)
the two title molecules to its g component are illustrated by g can be calculated from a2 using the following equation.
density analysis and quantified by g contribution decomposition.
 
The Cl4 in 3A25D2 possesses a devastating contribution to its x- hv
s2 ¼ a2 (A.4)
component of g relative to that for 3A25D4, while the y- NC
component of g only differs slightly between the two molecules.
The results have well explained the influence of the substitutional where hv is the energy of the excited photon in joules and
position of the chalcone on g and the corresponding third-order NC = NAC is the molecular number density in unit volume, NA is
NLO property. A higher NLO effect for 3A25D2 than 3A25D4 may Avogadro’s number, and C is the concentration of the sample
be attributed to its narrow optical gap, the electron-donating solution. The s2 is usually quoted in the units Goeppert–Mayer
ability of para-Cl, and the low aromaticity of the phenyl ring. This (GM), where 1 GM is 1050 cm4 s photon1.
paper shows the impact of the substitution position and the Using the OA Z-scan data, the excited state absorption cross-
medium toward the photophysical and NLO properties, thereby section (sex) can be determined by the following relation.
promoting the design of chalcone derivatives with superior NLO
2 2 3 3
response.
,
6 q0 7 6 q0 7
6 7 6 7
TOA ¼ ln61 þ  2 7 6  2 7 (A.5)
4 z 5 4 z 5
Author contributions 1þ
zR
1þ
zR
Conception and writing: Q. A. Wong and C. K. Quah; synthesis
and SCXRD: Q. A. Wong, H. C. Kwong and C. K. Quah; spectro- with q0 = sexa0F0Leff/2hv where F0 is the on-axis fluence at focus.
scopies: Q. A. Wong, X. A. Wong, Y.-F. Win; NLO data collec- The ground state absorption cross-section (sg) value is
tion: P. S. Patil, N. B. Gummagol and S. V. Rao; NLO analysis: Q. calculated by the following relation.
A. Wong, C. K. Quah and P. S. Patil; DFT computational studies:
Q. A. Wong and C. K. Quah. All authors reviewed the results and sg = a0/NC (A.6)
approved the final version of the manuscript. Non-linear refractive index coefficient (n2) is determined by the
following equation.
Conflicts of interest 
l

Df0

n2 ðcm2 W1 Þ ¼ (A.7)
There are no conflicts to declare. 2p I0 Leff

21948 | Phys. Chem. Chem. Phys., 2022, 24, 21927–21953 This journal is © the Owner Societies 2022
PCCP Paper

where Df0 is the one-axis phase shift at the focus and it is A.2. Static and frequency-dependent (hyper)polarizabilities
extracted by fitting the normalized closed aperture curve with The energy of a system can be written as a Taylor expansion
the following equation. with respect to the external electric field F.
  X 1 XX
z EðFÞ ¼ Eð0Þ  mi Fi  aij Fi Fj
4Df0 2! i j
z i
TCA ¼ 1 þ " 2 #"R 2 # (A.8)
z z 1 XXX
þ9 þ1  bijk Fi Fj Fk
zR zR 3! i j k

1 XXXX
where TCA is the normalized transmittance for the CA  g Fi Fj Fk Fl  .. . ; i; j; k;l ¼ fx;y; zg
Z-scan. 4! i j k l ijkl
The third-order non-linear susceptibility (w(3)) is a complex (A.15)
quantity, the absolute value of w(3) can be calculated using the
  qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 2
where mi, aij, bijk, and gijkl are tensor components of the dipole
formula wð3Þ  ¼ ½<ðwð3Þ Þ þ½=ðwð3Þ Þ . The real and imaginary moment, polarizability, quadratic, and cubic hyperpolarizabilities,
part of w(3) are determined by inserting the a2 and n2 values into respectively.
the equations.109 The electronic properties discussed in this paper are
expressed by the following equations. The magnitude of electric
   4e0 cn02  2 1  dipole moment is described as follows.
< wð3Þ ðo; o; o; oÞ m2 V2 ¼ 104 n2 cm W qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
3
(A.9) jmj ¼ mx2 þ my2 þ mz2 (A.16)

The averaged isotropic polarizability and anisotropy polariz-

 ability are defined as follows.
  2e0 c 2
n02
= wð3Þ ðo; o; o; oÞ m2 V2 ¼ 102 a2 ðcm W1 Þ 1 
3o hai ¼ axx þ ayy þ azz (A.17)
(A.10) 3

Da ¼
where e0 is the permittivity of free space, c is the speed of
light, n0 = 1.4305 is the DMF linear refractive index at room qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
1  2  2 
temperature, and o is the angular frequency of the light field pffiffiffi axx  ayy þ ayy  azz þðazz  axx Þ2 þ6 axy2 þ ayz2 þ axz2
2
(o = 2pc/l). In our experiments, we quote the non-linear (A.18)
susceptibilities in the Gaussian unit (esu).
Eqn (A.11) is used to convert the third-order susceptibility The magnitude of quadratic hyperpolarizability b and the
between the SI and Gaussian (esu) systems. projection of b on the dipole moment vector are determined
as follows.
  4p qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
wð3Þ m2 V2 ¼ wð3Þ ðesuÞ (A.11) jbj ¼ bx2 þ by2 þ bz2 (A.19)
ð3  104 Þ2

X mi bi
Therefore, the relation can be expressed numerically as follows. bvec ¼ (A.20)
i
jmj
ð3Þ n02  
wR ðo; o; o; oÞ ðesuÞ ¼ n2 cm2 W1 (A.12) where bi (i = x, y, z) is given by,
0:039451
1 X 
bi ¼ b þ bjij þ bjji (A.21)
3 j¼x;y;z ijj
1
w(3)
I (o; o, o, o) (esu) = 201.71ln02a2 (cm W ) (A.13)
The averaged isotropic cubic hyperpolarizability hgi is defined
The molecular cubic hyperpolarizability (g) are calculated by as follows.
the following equation.
1  
hgi ¼ g þ gyyyy þ gzzzz þ 2 gxxyy þ gxxzz þ gyyzz (A.22)
ð3Þ
w ðo; o; o; oÞ ðesuÞ 5 xxxx
gðo; o; o; oÞ ðesuÞ ¼ (A.14)
Nc L 4 All DFT calculations for 3A25D2 and 3A25D4 molecules are
accomplished via the Gaussian 09 software. The (hyper)polar-
where NC = NAC  103 is the molecular number density in izabilities are evaluated by analytical third energy derivatives.
unit volume, NA is Avogadro’s number, C is the concentration of The conversion factors of the polarizability, quadratic, and
the sample solution in mol L1, and L is Lorentz local field cubic hyperpolarizabilities between the SI and Gaussian systems
factor. are as follows.

This journal is © the Owner Societies 2022 Phys. Chem. Chem. Phys., 2022, 24, 21927–21953 | 21949
Paper PCCP

a (a.u.) = 1.6488  1041 a (C2 m2 J1) = 1.4819  1025 a (esu) 3 H. Meier, Conjugated oligomers with terminal donor–
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4 L. Beverina and G. A. Pagani, p-Conjugated zwitterions as
(A.24)
paradigm of donor–acceptor building blocks in organic-
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