Chemical Physics Impact 8 (2024) 100565

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Chemical Physics Impact

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Impact of Homocyclic and Heterocyclic Rings of Chalcones on Charge

Transfer Behaviour: A Nonlinear Optical Study
Nur Aisyah Mohamad Daud a, Qin Ai Wong a, *, Bi Sheng Ooi a, Ching Kheng Quah a, *,
Farah Diana Ramzi a, Yip-Foo Win b, Parutagouda Shankaragouda Patil c
a
X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, Penang 11800, Malaysia
b
Department of Chemical Science, Faculty of Science, Universiti Tunku Abdul Rahman, Perak Campus, Jalan Universiti, Bandar Barat, 31900 Kampar, Perak, Malaysia
c
Department of Physics, B.L.D.E. Association’s S.B. Arts and K.C.P. Science College, Vijayapura 586103, Karnataka, India

A R T I C L E I N F O A B S T R A C T

Keywords: This paper presents the effects of incorporating thienyl and phenyl rings as the terminal ring in the cinnamoyl
Nonlinear Optics counterparts of chalcones with donor-acceptor-donor (D-A-D) push-pull setting, on their photophysical re­
Density Functional Theory sponses. Two fluoro-methoxy substituted chalcone derivatives with distinct cinnamoyl systems, 4-methylthio­
Chalcones
phene-2-carbaldehyde (2F4MA48) and 2,4-dimethylbenzaldehyde (2F4MA96), were synthesized.
Intramolecular Charge Transfer
Z-scan
Characterization of these chalcone derivatives was performed using nuclear magnetic resonance (NMR), Fourier-
transform infrared (FTIR) and single-crystal X-ray diffraction (SCXRD). Comparative studies on the linear and
nonlinear optical responses were carried out through both experimental analyses and theoretical density func­
tional theory (DFT) calculations. The electronic absorption spectra computed using DFT were compared with the
UV-Vis spectra to elucidate the intramolecular charge transfer mechanism via the hole-electron distribution and
interfragmentary charge transfer analyses. Molecular properties were examined through electrostatic potential
(ESP) maps, π-electron localization function (ELF-π), and frontier molecular orbitals (FMOs). The incorporation
of thienyl ring is found to give a stronger push-pull effect and greater electron delocalization. Experimental
nonlinear optical responses were investigated using Z-scan technique with a continuous-wave incident laser at a
wavelength of 532 nm. Both compounds showed two-photon-induced reverse saturation absorption (RSA) and
self-defocusing responses. It was observed that the thienyl-based chalcone, exhibited greater optical nonlinearity
in terms of nonlinear absorption (NLA), nonlinear refraction (NLR), and optical limiting. The experimental third-
order nonlinear optical susceptibility (χ (3) ) was determined to be 8.04 × 10− 8 esu for 2F4MA48 and 1.08 × 10− 8
esu for 2F4MA96. The onset limiting threshold (FS) was found to be 2.63 kJ cm− 2 for 2F4MA48 and 5.23 kJ
cm− 2 for 2F4MA96. The steep optical limiting traces of 2F4MA48 show superior performance compared to
2F4MA96.

1. Introduction devices hinges on the understanding and utilization of NLO, it is

Nonlinear optics (NLO) is a phenomenon that arises from the
nonlinear relationship between the polarization of the materials and the
applied electric field, leading to changes in frequencies and phases of the
incident light [1]. NLO finds applications spanning diverse scientific and
technological domains including optical limiting, optical signal pro­
cessing, optical communication systems, and nonlinear imaging. Driven
by the need for faster computational speeds and broader bandwidth,
achievable by optical signals, there has been a substantial increase in
demand for NLO materials [2–4]. Since the development of all-optical
crucial to design materials that exhibit strong optical nonlinearity. For
that reason, structural-property relationships of novel NLO materials are
being extensively explored in both organic and inorganic materials
[5–11]. Inorganic materials, known for high thermal stability and good
mechanical strength, can be brittle due to their high density [12–14].
This brittleness limits the tunability of inorganic NLO materials to meet
specific requirements. In contrast, low-density organic materials offer
greater flexibility, enabling fine-tuning of their NLO responses [15,16].
Furthermore, organic materials are known for their relatively simple
synthesis process, ease of structural modification, and cost-effectiveness

* Corresponding author.
E-mail addresses: qinai940224@gmail.com (Q.A. Wong), ckquah@usm.my (C.K. Quah).

https://doi.org/10.1016/j.chphi.2024.100565
Received 8 December 2023; Received in revised form 15 February 2024; Accepted 10 March 2024
Available online 15 March 2024
2667-0224/© 2024 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-
nc/4.0/).
N.A. Mohamad Daud et al.
for mass production [17–20]. In addition to these practical advantages,
organic compounds also exhibit ultra-fast response, great nonlinear
refraction (NLR), excellent nonlinear absorption (NLA), and high laser
damage threshold [21,22].
Chalcone is a naturally occurring compound in plants, characterized
by general structure consisting of two aromatic rings linked by an
aliphatic three-carbon chain of α,β-unsaturated carbonyl system [23,
24]. The presence of alternating single and double bonds facilitates the
free movement of electrons across the molecules through overlapping
π-orbitals. This electron delocalization improves the NLO response of the
materials, making chalcone derivatives promising NLO materials. The
distinctive push-pull conjugated structure of chalcone derivatives adds
additional aspect that has garnered significant attention among re­
searchers for their multifaceted properties and wide-ranging applica­
tions across fields such as biology, pharmaceuticals, agriculture, and
nonlinear optics [25,26]. The introduction of specific electron-donating
(D) or electron-withdrawing (A) groups in D-π-D, D-π-A, D-A-D, or D-A-A
arrangements induces molecular polarization, thereby enhancing their
NLO capabilities [27–30]. This flexibility allows for precise fine-tuning
of the push-pull effects in chalcone derivatives to meet specific appli­
cation requirements. While the majority of studies on chalcone de­
rivatives are centred around structures based on the benzene unit [31],
such as anthracene [32,33], pyrene [34,35], phenanthrene [36], or
naphthalene [37], there has been only occasional exploration of het­
erocyclic derivatives [38,39]. However, there have been reports in
which replacing phenyl rings with thienyl rings has led to favourable
optoelectronic properties [40–43]. The electron-rich sulphur atom in the
thiophene unit increases polarizability, thus enhancing the NLO
response of the compounds [44,45]. Nevertheless, at the time of writing,
the Cambridge Structural Database (CSD) has recorded 5055
benzene-based chalcones, compared to only 514 thienyl-based chalcone,
according to the CCDC ConQuest search results (Version 5.44, June
2023).
In this view, a thienyl based chalcone, (E)-1-(2-fluoro-4-methox­
yphenyl)-3-(4-methylthiophen-2-yl)prop-2-en-1-one (2F4MA48) and a
benzene based chalcone, (E)-3-(2,4-dimethylphenyl)-1-(2-fluoro-4-
methoxyphenyl)prop-2-en-1-one (2F4MA96) were synthesized. Both
experimental measurement and theoretical computations were con­
ducted to examine their linear and nonlinear optical properties. The
results were compared for correlation and to understand the intra­
molecular charge transfer mechanism of thienyl and phenyl based
chalcones that contributes to these optical properties. To our knowledge,
this has not been studied in detailed by other research groups. Linear
and nonlinear optical experimental measurements were carried out
using UV-Vis spectroscopy and Z-scan technique, respectively. Whereas
the theoretical calculations were performed through density functional
theory (DFT) modelling. To further explore the extent of the structure-
property relationship, the charge transfer mechanism and molecular
properties were investigated using DFT through a comprehensive anal­
ysis of electrostatic potential (ESP) maps, π-electron localization func­
tion (ELF-π), frontier molecular orbitals (FMOs) and hole-electron
distribution for both chalcone derivatives.
2. Experimental
2.1. Synthesis and Crystallization
Compounds 2F4MA48 and 2F4MA96 were synthesized through a
crossed-Aldol reaction using the Claisen-Scmidt method. 2’-fluoro-4’-
methoxyacetophenone 1 (0.24 g, 1.4 mmol) with 4-methylthiophene-2-
carbaldehyde 2 (0.18 g, 1.4 mmol) (for 2F4MA48) or 2,4-dimethylben­
zaldehyde 3 (0.19 g, 1.4 mmol) (for 2F4MA96) were dissolved in 8 mL
methanol in a 50 mL round-bottom flask. The reaction was catalysed by
an aqueous solution of sodium hydroxide (10%) and the resulting
mixture was further stirred for six hours at room temperature inside a
fume cupboard. The precipitate obtained was rinsed with cold distilled
2
Chemical Physics Impact 8 (2024) 100565
water, filtered, and let to dry. Single crystals of 2F4MA48 and 2F4MA96
were grown through slow evaporation technique. The synthesis path­
ways are shown in Fig. 1.
(E)-1-(2-fluoro-4-methoxyphenyl)-3-(4-methylthiophen-2-yl)
prop-2-en-1-one (2F4MA48). Solvent for growing single crystal:
acetone; yield 78%; 1H NMR (400 MHz, CDCl3, δ, ppm): 7.87–7.80 (m,
2H, 5CH and 9CH), 7.23–7.19 (d, 1H, J = 16.0 Hz, 8CH), 7.14 (s, 1H,
13
C), 6.97 (s, 1H, 11CH), 6.77–6.75 (d, 1H, J = 8.0 Hz, 4CH), 6.64–6.62
(d, 1H, J = 8.0 Hz, 2CH), 3.85 (s, 3H, 14CH), 2.24 (s, 3H, 15CH); 13C NMR
(100 MHz, CDCl3, δ, ppm): 186.70, 186.66 (C7), 164.61, 164.49 (C3),
164.36, 161.83, (C1), 140.26 (C10), 139.07 (C12), 136.65 (C9), 134.02
(C13), 132.70, 132.66 (C5), 124.59 (C11), 124.08, 123.99 (C8), 119.79,
119.66 (C6), 110.85, 110.83 (C4), 102.01, 101.74 (C2), 55.94 (C14),
15.64 (C15); FT-IR (ATR (solid), ν, cm− 1): 3100 (sp2 C–H), 3012,2945,
2842 (sp3 C–H), 2969, 2924, 2861 (sp3 C–H), 1647 (C– –O), 1578 (En,
C–
–C), 1611, 1418 (Ar1, C– –C), 1541, 1438 (Ar2, C– –C), 977 (C–H),
1227, 1042 (C–O), 1098 (C–F), 868, 819 (Ph, C–H), 849, 738 (Th,
C–H), 839, 656 (C–S).
(E)-3-(2,4-dimethylphenyl)-1-(2-fluoro-4-methoxyphenyl)prop-
2-en-1-one (2F4MA96). Solvent for growing single crystal: acetone;
yield 84%; 1H NMR (400 MHz, CDCl3, δ, ppm): 8.08–8.04 (d, 1H, J =
16.0 Hz, 9CH), 7.90–7.86 (t, 1H, J = 8.0 Hz, 5CH), 7.60–7.58 (d, 1H, J =
8.0 Hz, 15CH), 7.37–7.33 (d, 1H, J = 16.0 Hz, 8CH), 7.04–7.03 (m, 2H,
12
CH and 14CH), 6.79–6.77 (d, 1H, J = 8.0 Hz, 4CH), 6.65–6.63 (d, 1H, J
= 8.0 Hz, 2CH), 3.86 (s, 3H, 16CH), 2.44 (s, 3H, 17CH), 2.33 (s, 3H,
18
CH); 13C NMR (100 MHz, CDCl3, δ, ppm): 187.39, 187.36 (C7), 164.59,
164.47 (C3), 164.40, 161.87 (C1), 141.61 (C9), 140.68 (C11), 138.50
(C13), 132.78, 132.74 (C5), 131.77 (C12), 131.16 (C10), 127.24 (C15),
126.69 (C14), 125.70, 125.62 (C8), 120.00, 119.88 (C6), 110.85, 110.83
(C4), 102.00, 101.73 (C2), 55.93 (C16), 21.46 (C18), 19.90 (C17); FT-IR
(ATR (solid), ν, cm− 1): 3085 (sp2 C− H), 2986, 2921, 2849 (sp3 C–H),
2968, 2953 (sp3 C–H), 1652 (C– –O), 1587 (En, C– –C), 1610, 1498 (Ar1,
C–
–C), 1610, 1498 (Ar2, C– –C), 975 (C–H), 1234, 1041 (C–O), 1094
(C–F), 873, 857, 822, 802 (Ph, C–H).
2.2. Characterization
2.2.1. Spectroscopy
1
H and 13C NMR were conducted on a JOEL JNM-ECX 400 FT-NMR
spectrometer at 400 MHz and 100 MHz, respectively, in deuterated
chloroform (CDCl3) with tetramethylsilane (TMS) as internal reference.
Proton and carbon resonances were reported as ‘s’ for singlet, ‘d’ for
doublet, and ‘m’ for multiplet. FTIR spectra were measured using a
Perkin Elmer Frontier FTIR Spectrophotometer with attenuated total
reflectance (ATR) sampling technique in the region of 4000–450 cm− 1
(4 scans). UV-Vis spectra were recorded using a Varian Cary 5000 UV-
Vis-NIR spectrophotometer in the range of 200–900 nm at 0.0001 M
concentration in n,n-dimethylformamide (DMF) solution. The mea­
surements were conducted with the samples contained inside 10 mm
quartz cells.
2.2.2. Single-Crystal X-ray Diffraction
The molecular structures of 2F4MA48 and 2F4MA96 were deter­
mined with single crystal X-ray diffraction (SCXRD) method at room
temperature. The selected crystals had dimensions of 0.193 mm × 0.225
mm × 0.428 mm for 2F4MA48 and 0.159 mm × 0.268 mm × 0.644 mm
for 2F4MA96. X-ray measurement was carried out using Bruker APEX II
DUO CCD area detector diffractometer with graphite-monochromated
Mo Kα radiation (0.71073 Å). The raw data were reduced using SAINT
program [46] and the empirical absorption were corrected with SADABS
program [46]. The structures were solved by intrinsic phasing method
and refined by full-matrix least-squares techniques with SHELXTL soft­
ware package [47,48]. Non-hydrogen atoms were refined with aniso­
tropic displacement coefficients while hydrogen atoms were positioned
geometrically and were assigned isotropic displacement coefficients
with riding model, Uiso (H) = 1.2 Ueq (C) or 1.5 Ueq (C). Molecular
N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

Fig. 1. Synthesis pathways of compounds 2F4MA48 and 2F4MA96.

graphics and publications materials were prepared using Mercury [49],
CrystalExplorer [50] and PLATON [48]. Crystal data, data collection and
structure refinement details are summarized in Table 1. The crystallo­
graphic information file (CIF) of 2F4MA48 and 2F4MA96 were depos­
ited to the Cambridge Crystallographic Data Centre (CCDC) and may be
retrieved with the deposition numbers CCDC: 2049735 and CCDC:
2049744, respectively.
2.2.3. Z-scan and Optical Limiting Studies
Third-order nonlinear optical responses were investigated through a
single beam Z-scan approach [51,52], employing open-aperture and
close-aperture techniques using a 532 nm continuous-wave diode-­
pumped solid-state (DPSS) operating at 200 mW. The samples (0.01 M)
were dissolved in DMF and contained within 1 mm thick quartz cells. To
focus the laser beam onto the samples, a 7 mm plano-convex lens with
Table 1
Summary of crystal data and refinement parameters of 2F4MA48 and
2F4MA96.
Compound 2F4MA48 2F4MA96
focal length of 0.25 m was used, resulting in a peak intensity (at focus),
I0 of 2.36 × 108 Wm− 2 and beam waist radius, ω0 of 23.0 μm. The
Rayleigh range, zR value was calculated at 3.18 mm, satisfying the thin
sample condition for Z-scan measurements as the sample thickness was
less than zR.
The measurements were conducted by scanning the quartz cells
containing samples, which were placed on a translation stage, as it
moved along the Z-axis (beam propagation direction) at a speed of 1.2
mm per second. Transmittance was recorded as a function of position
with respect to the focal length. Nonlinear absorption (NLA) co­
efficients, α2 were determined using open-aperture setup (without an
aperture), and nonlinear refraction (NLR) coefficients, n2 were evalu­
ated based on the ratio of close-aperture (a finite aperture in the far-
field) transmittance to open-aperture transmittance. Optical limiting
responses were extracted using open-aperture Z-scan data and using a
fluence equation as: F(z) = (2Ein )/[πω(z)2 ], where Ein is the input laser
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
energy and ω(z) = ω0 1 + (z/zR )2 is the beam radius at a given z-po­
sition along the beam.

CCDC deposition number; CCDC: 2049735; CCDC: 2049744; 2.3. Computational Details
CCDC entry FOHYOU FOHYUA
Molecular formula C15H13FO2S C18H17FO2
Molecular weight 276.31 284.32
2.3.1. Hirshfeld Surface Analysis
Crystal system Monoclinic Triclinic Hirshfeld surface analysis was conducted using CrystalExplorer21
Space group P21/n P1 program [50,53]. The calculations were performed using TONTO [54], a
a (Å) 6.62 4.84 built-in quantum chemistry program, at the calibrated DFT model of
b (Å) 12.09 7.92 B3LYP/6-311G(d,p) level of theory [55,56]. Hirshfeld surfaces mapping
c (Å) 16.28 19.32
α(◦ ) 90.00 98.09
properties over dnorm, shape index, and curvedness were generated, at
β (◦ ) 92.74 91.49 the standard high resolution. The expanded two-dimensional (2D)
γ(◦ ) 90.00 96.31 fingerprint plots of the individual intermolecular interactions were
V (Å3) 1300.60 728.20 plotted as de against di, where de and di refer as the distance from
Z 4 2
Hirshfeld surface to the external nuclei and internal nuclei, respectively.
Dcalc (g cm− 3) 1.411 1.297
Crystal dimensions (mm) 0.193 × 0.225 × 0.428 0.159 × 0.268 ×
0.644 2.3.2. Gaussian 09 Molecular Analysis
Crystal color, shape Brown, block Yellow, plate Theoretical computations were carried out using density functional
µ (mm− 1) 0.255 0.092 theory (DFT) with the Gaussian package; GaussView [57] and
Radiation, λ (Å) Mo Kα, 0.71073 Mo Kα, 0.71073
Tmin, Tmax 0.899, 0.952 0.7408, 0.9509
Gaussian09 [58] programs. The coordinates of the atom arrangement
Measured reflections 19570 17631 from SCXRD CIF file served as the stable starting model for geometry
hkl range − 8≤h≤8 -5 ≤ h ≤ 5 optimization. The optimized geometry was utilized for subsequent DFT
− 15 ≤ k ≤ 15 − 9≤k≤9 calculations. In all calculations, CAM-B3LYP functional [59–61] was
− 21 ≤ l ≤ 20 − 23 ≤ l ≤ 23
combined with 6-311++G(d,p) basis set [62]. DFT simulated 1H and 13C
θ limit (◦ ) 2.099 – 27.707 2.132 – 25.999
Unique reflections 3037 2848 NMR spectra were calculated using gauge-independent atomic orbital
Observed reflections [I > 2σ(I)] 1667 1655 (GIAO) method in chloroform solvent, with TMS as the internal refer­
Parameters 174 193 ence. Vibrational frequencies assignments were determined through
Goodness of fit on F2 1.016 1.018 potential energy distribution (PED) analysis of VEDA4 software [63] and
R [F2 > 2σ(F2)], wR(F2) 0.0544, 0.1317 0.0565, 0.1366
vibrational animation of GaussView [57]. Time-dependent DFT

3
N.A. Mohamad Daud et al.
(TD-DFT) was employed for computing electronic spectra [64,65] in
DMF solvent environment.
Nonlinear optical properties were investigated using CAM-B3LYP
and an additional B3LYP [58,66] functionals at the same level of the­
ory (6-311++G(d,p)) via derivative method and were performed in DMF
solvent environment for comparison purposes. The parameters deter­
mined included dipole moment (μ), polarizability (α), first hyper­
polarizability (β), and second hyperpolarizability (γ). Solvent-phase DFT
calculations were conducted via the integral equation formalism variant
of the Polarizable Continuum Model (IEFPCM). The choice of solvents;
chloroform and DMF were to match the experimental solvent conditions.
Analysis of the DFT-output results were performed using Multiwfn pro­
gram [67], while Visual Molecular Dynamic (VMD) [68] was used for
visualizing and rendering the graphical results.
3. Results and Discussion
3.1. NMR Analysis
The molecular structures and the number of hydrogen and carbon
atoms in 2F4MA48 and 2F4MA96 molecules are confirmed by 1H NMR
and 13C NMR analytical method. The 1H NMR and 13C NMR spectra of
both compounds are shown in Figs. S1–S4, whereas the experimental
and theoretical chemical shifts are listed in Table S1. The experimental
chemical shifts are slightly deviated from the theoretical values, but the
results are highly consistent, and the number of protons and carbons
present are in good agreement.
The proton NMR chemical shifts are towards downfield between
8.1–6.6 ppm for aromatic and trans hydrogens and towards upfield
(shielded) between 2.5–2.2 ppm for methylbenzene. The presence of
methoxy protons is confirmed by the occurrence of singlet centring at δ
≈ 3.85 ppm with an integration value of 3. In 2F4MA96, the presence of
the two vinylic hydrogens (Hα and Hβ) are signified by the two doublets
in the range of 7.37–7.33 ppm and 8.08–8.04 ppm for H8 and H9,
respectively. A similar pattern should be observed in 2F4MA48. How­
ever, the doublet signal of H9 overlapped with the triplet signal of H5
causing it to resolve into a multiplet between 7.88–7.80 ppm. For both
compounds, the presence of fluorine atom with nuclear spin of I = ½ led
to the coupling with both adjacent hydrogen and fluorine atoms,
resulting in doublet signal for H2 in 6.65–6.62 ppm and a triplet signal
for H5 between 7.90–7.83 ppm. The presence of methyl protons on the
thienyl ring in 2F4MA48 is determined as a singlet with integration
values of 3 at 2.25 ppm whereas the presence of alkyl protons on the
dimethyl phenyl ring in 2F4MA96 is denoted by the singlets at 2.33 ppm
and 2.44 ppm.
In 13C NMR spectra, the most downfield (deshielded) peaks centring
at δ ≈ 188–186 ppm confirmed the presence of the carbonyl carbon (C7).
A significant deshielding effect is observed at 165–161 ppm for C1 and
C3 that are directly bound to the fluorine atom and methoxy group
respectively, due to the nature of fluorine atom and methoxy groups that
are more electronegative than carbon atoms, decreasing the surrounding
electron density. The same effect is observed for aromatic carbon that is
attached to the methyl group which results in signals around 141–138
ppm, which is assigned to C12 for 2F4MA48 and C11 and C13 for
2F4MA96. The vinylic carbons (C8 and C9) are indicated by the char­
acteristic peaks of α-carbon and β-carbon between 126–124 ppm and
142–137 ppm, respectively. The aromatic carbons that are bridged with
enone moiety (C6 and C10) exhibits a medium and a weak intensity
signals around 120 ppm and 140–131 ppm, respectively, whereas the
remaining aromatic carbons are observed between 133–101 ppm. The
high field region is mainly assigned to the methyl carbons (22–15 ppm)
and methoxy carbons (~56 ppm) due to their weak resonance structure.
Carbon atoms in the proximity of fluorine atom shows splitting reso­
nance due to the strong and long-range fluorine-carbon couplings.
4
Chemical Physics Impact 8 (2024) 100565
3.2. FTIR Analysis
The molecular structures of 2F4MA48 and 2F4MA96 are further
validated by using FTIR experimentally and DFT computationally. The
spectra are presented in Figs. S5 and S6. The computed frequencies are
scaled by 0.958 and 0.983 for frequencies above and below 1800 cm− 1,
respectively [69]. The experimental and scaled DFT-computed FTIR
bands and their respective band assignments are in good agreement
(Table S2).
The C–H stretching modes are observed as medium intensity bands
in the standard region of 3100–2840 cm− 1. These bands correspond to
the C–H stretching of the aromatic rings and alkyl groups for wave­
number longer and shorter than 3050 cm− 1, respectively. Another
vibrational mode that is assigned to C–H bonds of the aromatic rings is
the out-of-plane bending between 900–690 cm− 1, which informs the
pattern of substitution. The medium intensity band near 873–822 cm− 1
and the strong intensity band near 857–802 cm− 1 in experimental
spectra of both compounds is attributed to C–H out-of-plane bending of
the 1,2,4-substituted benzene ring. For 2F4MA48, thienyl ring gives
characteristics absorption at 738 and 849 cm− 1. Meanwhile, the
stretching of the carbonyl group (C– –O) appeared as an intense and
unique band between 1652–1647 cm− 1 in experimental spectra and
between 1678–1675 cm− 1 in theoretical spectra. The intense stretching
is due to the large dipole moment between the large partial positive
charge of the carbonyl carbon and the large partial negative charge of
the oxygen atom.
The most intense absorptions are observed between 1611–1578
cm− 1 of the experimental spectra in both compounds, while the rela­
tively weaker vibrational bands are detected between 1541–1418 cm− 1.
These bands signify the stretching of C– –C bonds on the enone bridge
and the aromatic ring. The trans C– –C bond of the enone bridge is
indicated by the medium strength experimental band at 977 cm− 1 and
975 cm− 1 for 2F4MA48 and 2F4MA96, respectively. The stretching of
the aryl fluorine and the aryloxy group are demonstrated as strong bands
between 1098–1094 cm− 1 and 1234–1041 cm− 1, respectively. Addi­
tional vibrational mode is observed for 2F4MA48 at 839 and 650 cm− 1,
and is assigned to the C–S band stretching in the thienyl ring.
3.3. Single Crystal X-ray Diffraction and Hirshfeld Surface Analysis
2F4MA48 is crystallised in the centrosymmetric monoclinic crystal
system of space group P21/n and 2F4MA96 is crystallised in the
centrosymmetric triclinic crystal system of space group P1. The phenyl
ring (C1–C6) of 2F4MA48 and 2F4MA96 have a fluorine atom attached
to the ortho-position and a methoxy group attached to the meta-position
(Fig. 2). With respect to the π-conjugated carbon-carbon double bond
C8––C9, both molecules exist in trans configuration as suggested by the
torsion angle (C7–C8– –C9–C10) of nearly ±180◦ at 179.8◦ and -179.3◦
for 2F4MA48 and 2F4MA96, respectively. The phenyl ring (C1–C6) for
both compounds is almost co-planar with the corresponding aromatic
ring that is thienyl ring (S1/C10–C13), with a dihedral angle of 3.63◦ for
2F4MA48, and phenyl ring (C10–C15), with a dihedral angle of 3.92◦
for 2F4MA96.
In the crystal structure of 2F4MA48 (Fig. 3a), adjacent molecules
form centrosymmetric dimers via a pair of intermolecular C2—H2A⋅⋅⋅F1
hydrogen bonds (Table 2) with R22 (8) graph-sets motif. These dimers are
joined through C13—H13A⋅⋅⋅O1 hydrogen bond to form two-
dimensional corrugated sheets (Fig. 3b) and are further linked into
edge-to-edge fashions through the bifurcated C9—H9A⋅⋅⋅O2 and
C11—H11A⋅⋅⋅O2 hydrogen bonds with R12 (6) graph-set motif, forming a
three-dimensional (3D) packing. Viewing the 3D molecular packing
along c-axis shows the zig-zag packing arrangement (Fig. 3c) that are
further consolidated by C—H⋅⋅⋅π interaction between H15C and Cg2 at
the separation distance of 2.76 Å (Table 3). The parallel-displaced π⋅⋅⋅π
interactions between the molecules are very weak, with separation
N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

Fig. 2. Asymmetric units of (a) 2F4MA48 and (b) 2F4MA96 shown in 50% probability displacement ellipsoids with labels for non-hydrogen atoms.

distances between 4.28 to 5.75 Å. 2F4MA48 compared to 2F4MA96. The characteristic ‘wings’ feature in
The structural arrangement of 2F4MA96 involves centrosymmetric the plot of H⋅⋅⋅C/C⋅⋅⋅H is evidenced by the C–H⋅⋅⋅π interactions, sup­
dimers (Fig. 4a) formed by a pair of C16—H16A⋅⋅⋅O2 hydrogen bonds ported by the shape index and curvedness plots (Fig. S8). On the shape
(Table 2) with R22 (6) graph-set motif. These dimers are linked into two- index surfaces, the complementary pair of the red concave and blue
column infinite chains through C2—H2A⋅⋅⋅O1 hydrogen bond into side- convex region (circled in red) over the aromatic ring and hydrogen
by-side fashions, forming C22 (6) graph-set motif that are propagating in atoms imply the interplanar stacking arrangement by C–H⋅⋅⋅π interac­
b-axis direction (Fig. 4b). The two-column chains lie as two-dimensional tion. Whereas, on the curvedness surface, it is demonstrated by the light
sheets parallel to (1 0 4) and are stacked together (Fig. 4c) by the offset blue region (circled in red) over the aromatic ring and hydrogen atoms.
C18—H18C⋅⋅⋅Cg4 interactions (2.78 Å) (Table 3). Similarly to The Hirshfeld surface of 2F4MA48 is additionally contributed by S⋅⋅⋅H/
2F4MA48, the offset-displaced π⋅⋅⋅π interactions between the centroids H⋅⋅⋅S interaction from the thienyl ring at 8.6%.
of 2F4MA96 are very weak, with separation distances ranging from 4.84
to 5.84 Å. Additionally, both structures possess an intramolecular
3.4. Molecular Electronic Structure Analysis
C8—H8A⋅⋅⋅F1 hydrogen bond interaction with a S(6) graph-set motif
and comparable separation distance.
3.4.1. Molecular Electrostatic Potential
The Hirshfeld surfaces are calculated to visualize the intermolecular
The intermolecular interactions of 2F4MA48 and 2F4MA96 were
contacts within the crystal structures of 2F4MA48 and 2F4MA96. The
studied by examining their molecular electrostatic potential (ESP) maps
Hirshfeld surface mapped over the normalised contact distance dnorm are
of the vdW surfaces [70]. The ESP maps provide a visual representation
described in blue, white, and red colour scheme which represent distant
of the charge distribution within the molecule with red, white, and blue
contact, contact at approximate length with van der Waals (vdW) radii,
regions indicating negative, neutral, and positive electrostatic potential,
and short contact, respectively. In Fig. 5, the respective acceptor and
respectively. The generated ESP maps, along with the values of the
donor sites showing the strong intermolecular C–H⋅⋅⋅O and C–H⋅⋅⋅F
selected electrostatic potential for the surface minima and maxima are
hydrogen bonds, labelled as ① and ②, and ③, respectively, are revealed
presented in Fig. 6. From the ESP maps, the electrophilic attack sites are
on the Hirshfeld surface as red spots. Meanwhile, the bifurcated
around the vicinity of electron donating groups; oxygen, and fluorine
hydrogen bonds in 2F4MA48, the C9–H9A⋅⋅⋅O2 and C11–H11A⋅⋅⋅O2
atoms, displaying values ranging from -54.93 to -21.27 kcal mol− 1.
interactions appear as medium red spots (Fig. 5a: ②). The C–H⋅⋅⋅O
These regions of negative electrostatic potential arise from the presence
hydrogen bonds (Fig. 5b: ①,②) in 2F4MA96 are indicated by the bright
of lone pairs, with the oxygen atoms possessing two lone pairs and the
red spots of similar size due to the comparable separation distance of ~
fluorine atom exhibiting three lone pairs. Consequently, these areas
2.6 Å (Table 2). An additional red spot of C⋅⋅⋅H intercontact is revealed
exhibit a higher electron density, rendering them more susceptible to
for 2F4MA96 between C16 and H5A (Fig. 5b: ⑤). Meanwhile, the pale
electrophilic interactions. The most prominent red region surrounding
red spots labelled ④ represent the C–H⋅⋅⋅π short contacts that are
the carbonyl oxygen atom indicates the global minima with values
involved in the molecular stacking in both compounds.
-53.69 kcal mol− 1 for 2F4MA48 and -54.93 kcal mol− 1 for 2F4MA96,
The subsequent 2D fingerprint plots are developed to summarize the
suggesting a greater electron-withdrawing ability of the carbonyl group
contribution of individual intermolecular interaction on the Hirshfeld
relative to the methoxy group and fluorine atom. Meanwhile, the low
surface through de against di plot (Fig. S7). The fingerprint plots utilized
electron density hydrogen atoms are mainly associated with nucleo­
a blue-green-red colour scheme to visualize the relative scale of small,
philic attack sites (blue regions) with values ranging from 17.57 to 33.29
intermediate, and greatest contributions, respectively. The character­
kcal mol− 1. The positive electrostatic potential of both compounds
istic pair of sharp spikes representing the strong hydrogen bond is
shows a comparable charge distribution with the higher ESP values
observed for H⋅⋅⋅O/O⋅⋅⋅H interactions for both compounds. The H⋅⋅⋅O/
predominately surrounding the methoxy hydrogens. The analysis of
O⋅⋅⋅H pair of sharp spikes in 2F4MA96 is slightly shorter (de +
molecular electrostatic potential indicates that both compounds are in a
di ≃ 2.5Å) than those of 2F4MA48 (de + di ≃ 2.3Å), consistent with its
donor-acceptor-donor (D-A-D) push-pull system. The incorporation of
longer separation distance. In 2F4MA48, a second pair of sharp spikes at
an electron-rich thienyl ring has induced a significantly stronger
de + di ≃ 2.4Å, superimposed with the H⋅⋅⋅F/F⋅⋅⋅H interactions is
push-pull effect (33.29 kcal mol− 1 compared to 18.70 kcal mol− 1 at
spotted, signifying the C–H⋅⋅⋅F hydrogen bond. In 2F4MA96, the H⋅⋅⋅F/
relative sites) which could be the reason for the improved NLO prop­
F⋅⋅⋅H interactions appear as a pair of blunt spikes at de + di ≃ 3.0Å,
erties in 2F4MA48. These points of surface extrema are evidence of the
suggesting that the interaction does not portray hydrogen bonds nor
C–H⋅⋅⋅O and C–H⋅⋅⋅F chemical interactions within the compounds,
short intercontact. A short intermolecular H⋅⋅⋅H intercontact (de +
consistent with the Hirshfeld surface analysis in Section 3.3.
di ≃ 2.1Å) is observed in 2F4MA96, covering the most surface area at
Additionally, the contribution of each fragment: methylthienyl/
51.1%. Meanwhile, the H⋅⋅⋅H intercontact in 2F4MA48 shows a longer
dimethylphenyl, enone bridge, and fluoro-methoxyphenyl on the mo­
separation distance (de + di ≃ 2.4Å) and a smaller contribution of
lecular ESP was calculated via the quantitative molecular surface anal­
38.6%. The highly different contribution is attributed to the introduc­
ysis module [71]. The results are graphically presented in Fig. S9. The
tion of thienyl ring and relatively less amount of methyl group in
polar surface areas (|ESP|>10 kcal mol− 1) determined from the plots are

5
N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

Fig. 3. Structural arrangement of 2F4MA48 showing (a) R22 (8) centrosymmetric dimer, (b) two-dimensional corrugated sheet viewed along a-axis, and (c) three-
dimensional packing through bifurcated hydrogen bonds showing zig-zag structural arrangements along with C—H⋅⋅⋅π interactions, viewed along c-axis. Green
and blue dashed lines are intra- and intermolecular C—H⋅⋅⋅F hydrogen bonds. Magenta dashed lines are C—H⋅⋅⋅O hydrogen bonds and orange dashed lines are
C—H⋅⋅⋅π interactions.

191.27Å (61.26%) for 2F4MA48 and 199.80Å (59.11%) for 2F4MA96.
Noting that the benzoyl system in both compounds is similar, the higher
percentage of polar surface area in 2F4MA48 can be attributed to its
cinnamoyl system which is composed of sulphur atom. This difference
may arise from the greater polarity of the electron-rich thienyl ring
relative to the phenyl ring [72,73].
3.4.2. Electron Delocalization
The degree of π-electron delocalization in the molecules is assessed
using real space function and topology analyses based on electron

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N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

Table 2
Hydrogen-bonds geometry of 2F4MA48 and 2F4MA96 (Å, ◦ ).
Compound D—H⋅⋅⋅A D—H H⋅⋅⋅A D⋅⋅⋅A D—H⋅⋅⋅A Symmetry code

2F4MA48 C2—H2A⋅⋅⋅F1 0.93 2.58 3.479 163 -x, 1-y, 1-z

C13—H13A⋅⋅⋅O1 0.93 2.45 3.114 129 1/2+x, 3/2-y, 1/2+z
C9—H9A⋅⋅⋅O2 0.93 2.68 3.473 143 1/2-x, 1/2+y, 1/2-z
C11—H11A⋅⋅⋅O2 0.93 2.64 3.414 141 1/2-x, -1/2+y, 1/2-z
C8—H8A⋅⋅⋅F1 0.93 2.15 2.798 125
2F4MA96 C2—H2A⋅⋅⋅O1 0.93 2.62 3.525 165 x, -1+y, z
C16—H16A⋅⋅⋅O2 0.96 2.60 3.382 139 3-x, -y, -z
C8—H8A⋅⋅⋅F1 0.93 2.16 2.810 127

Table 3
C—H⋅⋅⋅π interactions geometry (Å, ◦ ).
Compound C—H⋅⋅⋅π C—H H—π C⋅⋅⋅π C—H⋅⋅⋅π Symmetry code

2F4MA48 C15—H15C⋅⋅⋅Cg2 0.96 2.76 3.664 157 2-x, 2-y, 1-z

2F4MA96 C18—H18C⋅⋅⋅Cg4 0.96 2.78 3.681 156 -1+x, y, z

*Cg2 and Cg4 are the centroid for S1/C10–C13 and C10–C15 rings, respectively.

localization function (ELF) [74]. The ELF-π isosurfaces, along with the
bifurcation points defined in the topology analysis framework, are
depicted in Fig. 7. A greater degree of electron delocalization within
ELF-π domains is indicated by the large value of bifurcation points and is
visually presented as continuous isosurfaces. The lower aromaticity of
the thienyl ring is demonstrated by the split ELF-π domains over the
sulphur atom, in contrast to the quasi-doughnut shape observed for
phenyl rings. This suggests a greater electron localization on the phenyl
ring of 2F4MA96 than on the thienyl ring of 2F4MA48. Consequently,
this inhibits the outward flow of electrons from the phenyl ring
compared to the thienyl ring. Accordingly, the splits between ELF-π
domains over the enone bridge for both compounds imply that electrons
are not easily delocalized from one end to the other. Yet, the high ability
of charge transfer flow through the cinnamoyl system compared to the
benzoyl system is characterized by the relatively high bifurcation values
of 0.42–0.56 at bonds C7–C8 and C9–C10 compared to 0.33 at band
C6–C7. Additionally, the larger bifurcation values over the enone
bridge in 2F4MA48 suggests that the delocalization of electrons from
both terminal ring to the carbonyl group is relatively easier than in
2F4MA96. Thus, the higher degree of π-electron delocalization in
2F4MA48 may result in a greater optical nonlinearity.
3.5. Frontier Molecular Orbitals (FMOs)
The chemical stability of 2F4MA48 and 2F4MA96 are evaluated
based on the frontier molecular orbitals (FMOs) from TD-DFT calcula­
tion [75]. The FMOs are decomposed into three fragments, and their
compositions are calculated (Table S3) using Hirshfeld weighting
function of Multiwfn program [76]. The three-dimensional (3D) plots of
the highest occupied molecular orbital (HOMO) and the lowest unoc­
cupied molecular orbital (LUMO) are presented in Fig. 8, along with the
energy level map of the three highest occupied and three lowest unoc­
cupied molecular orbitals. From the fragment composition plots; the
delocalization of HOMO primarily occurs on the methyl­
thienyl/dimethylphenyl ring at ~68%. Meanwhile, LUMO mainly lies
on the enone bridge at ~57% while also equally contributed by the
terminal rings at ~21% each. The calculated HOMO-LUMO gap is 5.88
eV for 2F4MA48 and 5.92 eV for 2F4MA96. The slightly smaller value
for 2F4MA48 can be attributed to the presence of a heteroatom in the
terminal ring of the molecule. The more electronegative sulphur atom,
compared to carbon, leads to an asymmetrical distribution of electron
density due to sulphur’s electron-withdrawing behaviour [77,78].
Moreover, the lone pair from sulphur contributes to additional electron
delocalization [79,80] by interacting with the π-electron in the mole­
cule, lowering the energy levels for LUMO [81]. This suggests that
2F4MA48 is more chemically reactive than 2F4MA96, potentially
leading to a higher optical hyperpolarizability.
3.6. Linear Absorption Studies
3.6.1. UV-Vis Spectroscopy
The linear absorption spectra are experimentally measured using
ultraviolet-visible (UV-Vis) spectroscopy in DMF solution and are
theoretically computed by using TDDFT [65]. Both the experimental and
theoretical absorption spectra are plotted in Fig. 9, and they show a close
agreement. The absorption spectra of both compounds exhibit two ab­
sorption maxima, as expected for chalcone [82,83], with the prominent
band (band I) located between 329 nm and 351 nm, and the second
slightly weaker band (band II) located between 264 nm and 308 nm.
Both bands are attributed to π→π* electronic transitions [84]
throughout different moieties of chalcone; where band I is due to the
absorption of the cinnamoyl group, while band II is due to the absorp­
tion of the benzoyl group. This is supported by the hole-electron dis­
tribution analysis (Section 3.6.3). 2F4MA48 shows a tiny bathochromic
shift in band I absorbance compared to 2F4MA96, implying that both
compounds require similar energy for electronic transition. Meanwhile,
in terms of the absorbance intensity of band I, 2F4MA96 is slightly
greater than 2F4MA48 due to the higher aromaticity of the phenyl ring
relative to the thienyl ring, which increases the intensity of π→π*
transitions.
Tauc’s plot is used to estimate the optical energy gap, Eg , while the
extrapolation of the experimental spectra is carried out based on relation
(1):
( )12
α0 hν = C hν − Eg (1)
where C is a constant, h is Planck’s constant, ν is the frequency of the
incident photons and α0 is the optical absorption coefficient; α0 =
2.303 × (A /d), A is the absorbance and d is the thickness of the sample.
1
The plot of (α0 hν)2 against photon energy (hν) for both compounds is
shown in Fig. 9 (insert graphs). The Eg are determined to be 3.21 eV and
3.42 eV for 2F4MA48 and 2F4MA96, respectively, and this trend is
consistent with the HOMO-LUMO energy gap. The cut-off wavelength is
determined by extrapolating the straight-line portion of the higher en­
ergies experimental band I absorbance peak. The cut-off points are 401
nm for 2F4MA48 and 377 nm for 2F4MA96.
3.6.2. Interfragmentary Charge Transfer Analysis
The contribution of each fragment towards the linear absorption
spectra is analysed via charge-transfer spectrum of interfragmentary

7
N.A. Mohamad Daud et al.
Fig. 4. Structural arrangement of 2F4MA96 showing (a) R22 (6) centrosymmetric dimer, (b) a pair of one-dimensional two-column chains, propagating along b-axis
direction, and (c) three separated layers joined by C—H⋅⋅⋅π interaction. Magenta and green dashed lines are intermolecular C—H⋅⋅⋅O and intramolecular C—H⋅⋅⋅F
hydrogen bonds, respectively. Orange dashed lines are C—H⋅⋅⋅π interactions.
charge transfer (IFCT) analysis [85]. The electronic transition is shown
as discrete spikes below the spectra relative to the oscillator strength
(Fig. 10). The band I absorption peak in both compounds is attributed to
the same S0 → S1 excitation, primarily from HOMO → LUMO electronic
transition. The IFCT plot reveals that this transition is predominantly
characterized by charge transfer and charge redistribution associated
with the respective cinnamoyl systems; transfer from methylthienyl ring
(Me-Th) in 2F4MA48 and dimethylphenyl ring (Me2-Ph) in 2F4MA96 to
the central carbonyl group, and followed by charge redistribution on
enone bridge and corresponding aromatic ring (Me-Th or Me2-Ph).
Conversely, band II originates from the doubly degenerate S0 → S3
and S0 → S4 excitations in 2F4MA48, and solely S0 → S4 excitation in
2F4MA96. For 2F4MA48, the doubly degenerate excitations involve
contributions from the entire molecule, representing a mix of charge-
transfer spectrum between the cinnamoyl and benzoyl systems, with a
slightly greater contribution from the former. In contrast, for 2F4MA96,
it is due to the charge redistribution and charge transfer pertaining to
8
Chemical Physics Impact 8 (2024) 100565
the benzoyl system. The S0 → S3 excitation is mainly contributed by
HOMO-1 → LUMO accounting for 92% contribution, while S0 → S4
excitation is mainly due to HOMO-2 → LUMO at 83% contribution. The
main electronic transitions contributing to the linear absorption spectra
are listed in Table 4 along with their corresponding excitation energies,
excitation wavelength, oscillator strength and orbital contributions.
In addition, the charge-transfer length (Δr) during electronic exci­
tations is calculated to determine the suitability of the functionals cho­
sen for DFT calculations. The assessment is based on whether the
electronic excitation occurs in short-range (Δr ≤ 1.5 Å) or long-range
(Δr ≥ 2.0 Å) [86]. From Table 4, the Δr values for all primary elec­
tronic transitions are found to be greater than 2.0 Å, implying that the
charge-transfer excitations are long-range. As a result, it is necessary to
choose the long-range corrected functionals with a high composition of
Hartree-Fock exchange component (≥ 33%) [86]. This shows the rele­
vance of employing CAM-B3LYP functional, which has 65% of
Hartree-Fock exchange composition, in this study.
N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

Fig. 5. Intermolecular interaction of (a) 2F4MA48 and (b) 2F4MA96 visualized by Hirshfeld surfaces plotted over dnorm.

Fig. 6. Molecular electrostatic potential (ESP) map of the vdW surface of (a) 2F4MA48 and (b) 2F4MA96. Points of surface minima and maxima are shown as dots
and labelled with the corresponding ESP values (kcal/mol) in red and blue, respectively.

Fig. 7. ELF-π isosurfaces of (a) 2F4MA48 and (b) 2F4MA96 with the bifurcation points indicated by the orange spheres and labelled for selected points (isovalue
of 0.7).

3.6.3. Hole-electron Distribution Analysis
The path of the intramolecular charge transfer (ICT) of the electronic
excitations is investigated using hole-electron analysis [84]. It is visu­
alized as ‘electron’ (yellow isosurface) and ‘hole’ (grey isosurface) to
signify the increment and decrement of electron density, respectively
(Fig. 11). The distributions are quantitatively characterized [87] to
distinguish between the local excitation (LE) and the charge-transfer
(CT) electron excitations (Table 5). The D index refers to the total
magnitude of the CT length, the Sr index describes the overlapping
extent of hole and electron (upper limit is 1.0), the H index is the overall
measure of the spatial extension of hole and electron distribution in x, y,
z, and CT directions, the t index describes the separation degree of hole
and electron in CT direction, ECoul signifies the hole-electron Coulomb
attractive energy, whereas HDI and EDI refer to hole and electron
delocalization indices, respectively. For S0 → S1 excitation, the D index
of both compounds is slightly larger than the average C–C bond length
(≃1.5 Å), supported further by an Sr index of ~ 0.7, indicating that more
than 70% of hole and electron are overlapping. Moreover, t index below
0 indicates that the separation between electron and hole distributions
are indistinct. By taking all these analyses into account, S0 → S1

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N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

Fig. 8. Frontier molecular orbitals and fragment composition plots of (a) 2F4MA48 and (b) 2F4MA96 (isovalue of 0.05).

Fig. 9. UV-Vis absorption spectrum of (a) 2F4MA48 and (b) 2F4MA96 and Tauc’s plot (insert graphs) showing the optical energy gaps. The solid blue lines represent
the experimental UV-Vis spectra while the dashed red lines represent DFT-simulated spectra.

Fig. 10. Electronic absorption spectra (black) of (a) 2F4MA48 and (b) 2F4MA96. The charge-transfer spectrum is shown in coloured lines. The peak positions of the
absorption bands (λmax ) are labelled for each band. The oscillator strength of the selected electronic transitions (major contribution for absorption bands) is shown as
distinct spikes and labelled with Roman numerals.

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N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

Table 4 gap of both compounds (see Section 3.6.1) is larger than the energy of a
The excitation energy, Eex , absorption wavelength, λex , oscillator strength, f0 , single photon (2.33 eV) but lower than the combined energy of two
and charge transfer length, Δr of electronic transitions from ground state, S0 to photons (4.66 eV) at wavelength of 532 nm, suggesting the involvement
excited state, Sn with the percentage contribution of FMOs electronic transition of 2PA process. To characterize the efficiency of the 2PA transition, the
in 2F4MA48 and 2F4MA96. value of 2PA cross-section, σ 2 is calculated using Eq. A.4. The greater σ2
S0 →Sn Eex (eV) λex (nm) f0 Δr (Å) Major contribution ( > 10%) value observed for 2F4MA48 is consistent with its stronger NLA
2F4MA48 response.
S0 →S1 3.61 343.49 0.75 2.91 H→L (93.6%) In the 2PA process, two photons can be absorbed either simulta­
S0 →S3 4.37 284.00 0.22 3.53 H − 1→L (92.2%) neously (referred to as genuine 2PA) or sequentially, with one photon
S0 →S4 4.70 263.65 0.16 3.46 H − 2→L (83.3%)
excites the electron to a near-resonant state (known as a virtual inter­
2F4MA96
S0 →S1 3.64 340.63 0.93 2.83 H→L (94%) mediate state) and another photon facilitating the electron transition to
S0 →S4 4.67 265.63 0.20 3.48 H − 2→L (83.1%) a higher energy level. In the latter 2PA case, an ESA process is involved,
leading to the depletion of the ground state [90–92]. To determine if the
ESA process is involved, the excited-state and ground-state absorption
excitation is determined to be LE type. Similarly, S0 → S4 excitation is cross-sections (σ ex and σg ) are calculated using Eqs. A.5 and A.6,
also regarded as LE type, evidenced by the overlapping between the respectively. σg of 2F4MA48 and 2F4MA96 are 4.19 × 10− 21 and 1.33 ×
distribution of hole and electron. In contrast, S0 → S3 excitation of 10− 21 cm2 whereas σex of 2F4MA48 and 2F4MA96 are 1.25 × 10− 21 and
2F4MA48, involving the thienyl ring which is absent in 2F4MA96, is 0.61 × 10− 21 cm2, respectively. For both compounds, σ ex values are
attributed to CT excitation based on the high degree of separation found to be smaller than σ g values, indicating that ESA does not
indicated by a positive t index. significantly contribute to the NLA property. Therefore, the NLA prop­
erty is determined to be a result of genuine 2PA.
3.7. Nonlinear optical studies In closed-aperture (CA) Z-scan, the peak-to-valley configuration
signifies the negative NLR property, a self-defocusing effect. However, in
3.7.1. Nonlinear Absorption (NLA) and Nonlinear Refraction (NLR) laser-material interactions, continuous wave laser can lead to thermal-
Z-scan technique is employed to investigate the third-order nonlinear effect-built-up due to the slow response time which results in negative
optical response under 532 nm continuous-wave laser domain. The nonlinearity. H. Y. Tan et al. [93] demonstrated the thermal lens effect
open-aperture and closed-aperture Z-scan data are fitted to the Sheik caused by temperature and refractive index gradient arising from local
Bahae model (see Appendix) [51,52] following relations A.1 and A.2, heat accumulation. Meanwhile, Maurya et al. [94] presented the influ­
respectively. The fitted data are presented in Fig. 12. Subsequently, ence of thermal effects on the nonlinear refractive index. Their findings
based on Sheik Bahae’s theory, the nonlinear absorption (NLA) coeffi­ suggest that thermal effect primarily affects NLR property and not NLA
cient, α2 , and the nonlinear refraction (NLR) coefficient, n2 are extrac­ property. S. M. Mian et al. [95] demonstrated the impact of localized
ted. This Z-scan experiment is characterized as an off-resonant process, heating on NLR property and proposed that a positive deviation of the
as both compounds exhibit transparency across visible and infrared peak-valley separation from Kerr value of 1.7zR was due to thermal
ranges, with cut-off points at 401 nm and 377 nm for 2F4MA48 and contributions. In our study, we found that the separation between the
2F4MA96, respectively (see Section 3.6.1). The NLO parameters of both peak and valley of the CA graph is indeed greater than 1.7zR, indicating
compounds, including NLA and NLR coefficients, real and imaginary
parts as well as the absolute third-order NLO susceptibility, molecular
second hyperpolarizability, two-photon absorption cross-section, Table 5
ground and excited state absorption cross-section, and thermal-optical Quantitative indices defined in the hole-electron analysis framework of com­
pounds 2F4MA48 and 2F4MA96.
coefficient are listed in Table 6. In open-aperture (OA) Z-scan, the
presence of the valley at z = 0 indicates a positive NLA response, a S0 →Sn D(Å) Sr (a.u.) H(Å) t(Å) ECoul (eV) HDI EDI
reverse saturable absorption (RSA) process. The deeper valley observed 2F4MA48
for 2F4MA48 compared to 2F4MA96 suggests a stronger NLA response, S0 →S1 1.90 0.70 2.99 -0.51 4.93 7.92 7.83
as indicated by the larger α2 value. In NLO materials, NLA response can S0 →S3 2.53 0.56 2.73 0.44 4.72 9.21 7.77
2.27 0.68 2.98 -0.28 4.88 8.86 7.81
result from various photon absorption mechanisms, such as two-photon
S0 →S4
2F4MA96
absorption (2PA), excited state absorption (ESA), multiple-photon ab­ S0 →S1 1.83 0.71 3.05 -0.66 4.99 7.64 7.93
sorption (MPA), free carrier absorption, nonlinear scattering, or a S0 →S4 2.33 0.66 2.93 -0.16 4.88 9.02 7.89
combination of these processes [88,89]. However, the optical energy

Fig. 11. Hole-electron distribution of the main excited transitions contributing to bands I and II linear absorption peaks of 2F4MA48 and 2F4MA96. Yellow and grey
isosurfaces represent the increment (electron) and decrement (hole) of electron density, respectively (isovalue of 0.002).

11
N.A. Mohamad Daud et al.
Fig. 12. (a) Open-aperture and (b) closed-aperture Z-scan curves of 2F4MA48 (blue) and 2F4MA96 (red), under 532 nm continuous wave laser domains. The dotted
lines depict the theoretical fits of Sheik Bahae’s formalism while the scattered plots represent the experimental data.
the presence of thermal lensing effect in the NLR response. This thermal
lens effect arises from variations in the medium’s refractive index with
( )
temperature n = n0 + dT dn
T . To compare the significance of thermal
effects in both compounds, the thermal-optical coefficient, dT dn
is calcu­
lated using relation A.7. The values are -7.63 × 10− 3 K− 1 for 2F4MA48
and -2.97 × 10− 3 K− 1 for 2F4MA96. The larger magnitude of dT
2F4MA48 may explain its stronger self-defocusing effect relative to
2F4MA96 and it is consistent with its more prominent CA scan trace
depth and greater n2 .
From α2 and n2 values extracted based on Sheik Bahae theory, the
real, ℜ(χ (3) ) and imaginary, ℑ(χ (3) ) parts of third-order susceptibility,
χ (3) ( − ω; ω, ω, − ω) are calculated by using Eq.s A.8 and A.9, respec­
tively. Afterwards, the absolute value of χ (3) are determined by applying
Eq. (2):
⃒ (3) ⃒ √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
⃒χ ( − ω; ω, ω, − ω)⃒ = [ℜ(χ (3) )]2 + [ℑ(χ (3) )]2
The χ (3) values are found to be 8.04 × 10− 8 esu and 1.08 × 10− 8 esu
for 2F4MA48 and 2F4MA96, respectively. Following χ (3) , the molecular
second hyperpolarizability, γ( − ω; ω, ω, − ω) is calculated using Eq.
(3):
χ (3) ( − ω; ω, ω, − ω)
γ( − ω; ω, ω, − ω) =
Nc L 4
where Nc = NA C × 10− 3 is the molecular number density in unit volume,
NA is Avogadro’s number, C is concentration of the sample solution in
mol L− 1, and L is Lorent local field. The γ values are found to be 3.98 ×
10− 27 and 1.08 × 10− 27 esu for 2F4MA48 and 2F4MA96, respectively.
Notably, the larger χ (3) and γ of 2F4MA48 indicate the greater optical
nonlinearity compared to 2F4MA96, accordant to the presumption that
a smaller optical energy gap leads to better NLO responses. The
enhanced optical nonlinearity in 2F4MA48 can be attributed to the
presence of a sulphur atom in one of the terminal aromatic rings, which
improves its electron-withdrawing capabilities and, consequently, in­
creases the polarity of the compound [96]. Additionally, the stronger
push-pull effect and lower aromaticity of thienyl ring in 2F4MA48
compared to phenyl ring in 2F4MA96, are another contributing factors.
As a result, 2F4MA48 exhibits greater intramolecular charge transfer to
central carbonyl group from both terminal rings: benzoyl ring with the
strong donor − OCH3 group and thienyl ring with weak donor CH3
group, inducing a larger polarization and promoting the NLO response
Chemical Physics Impact 8 (2024) 100565
of the compound. This finding aligns with the discussion in the ELF-π
analysis (Section 3.4.2) which has demonstrated that the degree of
electron delocalization between terminal aromatic rings in 2F4MA48 is
greater than that in 2F4MA96.
3.7.2. Optical limiting and Figures-of-Merits
dn
for
Since both compounds exhibit RSA responses, wherein the amount of
transmitted light decreases as the intensity of incident laser light in­
creases, these compounds could potentially be used as optical limiters to
protect sensitive optical components or the naked eye from high-
intensity irradiance [97,98]. Therefore, to evaluate their potential, the
optical limiting response of 2F4MA48 and 2F4MA96 is measured using
the open-aperture Z-scan technique with input intensities of a 532 nm
CW incident laser in DMF solution. The plot of normalized transmittance
against input fluence is presented in Fig. 13. From the plot, it is clearly
portrayed that 2F4MA48 demonstrates superior optical limiting
(2) behaviour compared to 2F4MA96. The steep slope observed in the
2F4MA48 trace blocks 12% of transmittance at the maximum input
fluence recorded (23.9 kJ cm− 2). In contrast, 2F4MA96 limits only up to
2% of transmittance at the same input fluence. The specific input fluence
at which transmittance begins to attenuate due to nonlinear process is
referred to as the onset limiting threshold (FS) [99]. The values obtained
are 2.63 kJ cm− 2 for 2F4MA48 and 5.23 kJ cm− 2 for 2F4MA96. The
(3) smaller FS of 2F4MA48 is consistent with its higher 2PA cross-section
analysis [90,92], suggesting that it has the ability to provide a faster
response in limiting light by attenuating it at lower intensities. Consis­
tently, the optical limiting threshold (FOL) which is the input fluence at
which the transmittance is 50% of linear transmittance, is determined to
be 5.32 kJ cm− 2 and 5.55 kJ cm− 2 for 2F4MA48 and 2F4MA96,
respectively. The lower FOL value of 2F4MA48 suggests its capability to
limit transmitted light at a lower input intensity. These findings align
with the greater optical nonlinearity of 2F4MA48 compared to
2F4MA96.
The optical limiting thresholds of the studied compounds were
compared with values reported for both thienyl and phenyl based
chalcone derivatives under the same experimental conditions of a 532
nm continuous wave laser domain (Table 7). It is observed that the
majority of reported FOL values for thienyl based chalcones are notice­
ably smaller than those of phenyl based chalcones, implying their better
performance. The lowest value is 1.67 kJ cm− 2, as presented by V. S.
Naik et. al. for 1-(5-bromo-2-thienyl)-3-(4-bromophenyl)prop-2-en-1-
one (B5B2SC). In their study, V. S. Naik et al. have also recorded FOL
12
N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

K− 1 )
5
(10−

-7.66
-2.98
dT
dn
cm2)
21
σex(10−

1.25
0.61
cm[2])
21
σg(10−

4.19
1.33
GM)

Fig. 13. Optical limiting response of 2F4MA48 (blue) and 2F4MA96 (red)
8
σ2 (10−

under 532 nm continuous wave laser domain. The continuous lines are the
9.06
1.63

theoretical fits, and the scattered plots are the experimental data.
esu)

Table 7
27

The optical limiting threshold (FOL) of 2F4MA48 and 2F4MA96 with several
γ(10−

3.98
0.53

reported chalcone derivatives under CW regime at 532 nm.

Compound Crystal Name C FOL (kJ Ref.
(M) cm− 2)
esu)

2F4MA48 1-(2-fluoro-4-methoxyphenyl)-3-(4- 0.01 5.32 Present

8

methylthiophen-2-yl)prop-2-en-1-
χ(3) (10−

8.04
1.08

one
Nonlinear optical parameters of 2F4MA48 and 2F4MA96 in DMF solution under 532 nm continuous wave domain.

2F4MA96 3-(2,4-dimeth ylphenyl)-1-(2-fluoro- 0.01 5.55 Present

4-methoxyphenyl)prop-2-en-1-one
F3BC 1-(3-bromophenyl)-3-(4- 0.01 7.41 [100]
esu)

fluorophenyl) prop-2-en-1-one
DA-ANC 1-(anthracen-9-yl)-3-(4- 0.01 6.47 [101]
8
ℑ (χ (3) )(10−

(dimethylamino)phenyl)prop-2-en-
1-one
3.23
0.58

3CAMC 1-(4-aminophenyl)-3-(3- 0.01 6.13 [102]

chlorophenyl) prop-2-en-1-one
3CAMC 1-(4-aminophenyl)-3-(3- 0.05 2.84 [102]
chlorophenyl) prop-2-en-1-one
esu)

B5B2SC 1-(5-bromo-2-thienyl)-3-(4- 0.01 1.67 [103]

8

bromophenyl) prop-2-en-1-one
ℜ (χ (3) )(10−

3C5B2SC 1-(5-bromo-2-thienyl)-3-(3- 0.01 7.38 [103]

chlorophenyl) prop-2-en-1-one
-7.36
-0.91

2M5B2SC 1-(5-bromo-2-thienyl)-3-(2- 0.01 3.17 [103]

methoxyphenyl) prop-2-en-1-one
TTMP 1-(thiophen-2-yl)-3-(3, 4, 5-trime­ 0.01 5.38 [29]
thoxyphenyl) prop-2-en-1-one
cmW− 1 )

I 3-(4-bromo-2-fluorophenyl)-1-(3,4- 0.02 5.45 [104]

dimethoxyphenyl)prop-2-en-1-one
II 3-(4-bromophenyl)-1-(3,4- 0.02 9.89 [104]
10

dimethoxyphenyl)prop-2-en-1-one
n2 (10−

-14.1
-1.74

i 2-chloro-4-fluoro-2’-hydroxy-4’,5’- 0.01 20.20 [18]

methylchalcone
ii 2-chloro-4-fluoro-2’,5’- 0.01 17.80 [18]
cmW− 1 )

dichlorothienyl chalcone
iii 2-chloro-4,6’-difluoro-4’- 0.01 11.10 [18]
methoxychalcone
5
α2 (10−

14.60
2.62

values for two other 5-bromo-2-thienyl based chalcones; 3.17 cm− 2

(2M5B2SC) and 7.38 kJ cm− 2 (3C5B2SC). Meanwhile, D. Haleshappa
et al. reported a value of 5.38 kJ cm− 2 for 1-(thiophene-2-yl)-3-(3, 4, 5-
α0 (m− 1 )

trimethoxyphenyl)prop-2-en-1-one (TTMP), which is slightly larger

2.52
0.80

than the thienyl based chalcone in this study (2F4MA48). For phenyl
based chalcone, previously reported values in literature include 7.41 kJ
Compound

cm− 2 for 1-(3-bromophenyl)-3-(4-fluorophenyl)prop-2-en-1-one

2F4MA48
2F4MA96

(F3BC), 6.47 kJ cm− 2 for 1-(anthracen-9-yl)-3-(4-(dimethylamino)

Table 6

phenyl)prop-2-en-1-one (DA-ANC), 6.13 kJ cm− 2 (0.01 M) and 2.84

13
N.A. Mohamad Daud et al.
(0.05 M) for 1-(4-aminophenyl)-3-(3-chlorophenyl)prop-2-en-1-one
(3CAMC), 5.45 kJ cm− 2 (0.02 M) for 3-(4-bromo-2-fluorophenyl)-1-
(3,4-dimethoxyphenyl)prop-2-en-1-one (I), 9.89 kJ cm− 2 (0.02 M) for 3-
(4-bromophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one (II), 20.2 kJ
cm− 2 for 2-chloro-4-fluoro-2’-hydroxy-4’,5’-methylchalcone (i), and
11.10 kJ cm− 2 for 2-chloro-4,6’-difluoro-4’-methoxychalcone (iii).
Additionally, A. Ekbote et al. demonstrated the effect of concentration
on the optical limiting response of 3CAMC at 0.01 M and 0.05 M.
Considering the concentration of the samples, 2F4MA96 is determined
to be the best optical limiter among the phenyl based chalcones in the
comparison. Nevertheless, thienyl based chalcones exhibit a clear su­
periority against phenyl based chalcones.
Figures-of-merits (FOMs) are used to assess their potential for all-
optical switching applications, utilizing the nonlinear absorption coef­
ficient, α2 and nonlinear refraction coefficient, n2 (see Section 3.7.1).
For a material to be considered suitable for such applications, it should
fulfil the two limits following relations (4) and (5):
n2 I0
one − photon FOM, W = ≫1
α0 λ
α2 λ
two − photon FOM, T = ≪1
n2
The studied compounds are determined to have satisfied the two
limits, and therefore are considered as potential materials for all-optical
switching devices operating under CW laser input.
3.7.3. Static and Dynamic (Hyper)polarizabilities
To further investigate the relationship between molecular structure
and optical nonlinearity, DFT method is employed. When calculating
(hyper)polarizabilities of chalcones, it is commonly reported in the
literature that the B3LYP functional is used. However, the long-range
corrected B3LYP, as proposed by Tawada et al. [61], referred as
CAM-B3LYP, is known for its relatively better performance in estimating
hyperpolarizabilities due to its higher percentage of the exchange en­
ergy term [105,106]. Nonetheless, both functionals are associated with
different issues. B3LYP is known to overestimate (hyper)polarizabilities
[107], while CAM-B3LYP is associated with issues related to low-lying
charge transfer (CT) energies [108,109]. Therefore, both functionals
are employed to study the static and dynamic (hyper)polarizabilities of
2F4MA48 and 2F4MA96. The dynamic NLO parameters are computed
at 532, 637, 655, 800, 1064, 1274 and 999999 nm incident wave­
lengths. The DFT-estimated parameters are dipole moment (μ), isotropic
Fig. 14. (a) Isotropic and (b) anisotropic static and dynamic polarizabilities of 2F4MA48 and 2F4MA96.
Chemical Physics Impact 8 (2024) 100565
polarizability 〈α〉, anisotropic polarizability (Δα), projection of first
hyperpolarizability on dipole moment (βvec ), and the average of second
hyperpolarizability 〈γ〉 (for related formulas, see Appendix B).
The frequency-dependent (hyper)polarizabilities are visualized as
3D trajectories in Figs. 14–16, and their values are given in Table S4-
S10. The calculated parameters are found to exhibit consistent trend of
decreasing (hyper)polarizabilities with increasing incident wavelengths,
and converging at static limit [19]. This relationship between (hyper)
polarizabilities and external frequency is attributed to the optical reso­
nance effect [110]. Values calculated using B3LYP are indeed larger
than those calculated using CAM-B3LYP for all parameters [107]. The
total dipole moments of 2F4MA48 and 2F4MA96 fall within the range
of 4.57 to 5.34 Debye, with the major components directed from μy ,
along the negative y-axis (Fig. S10). In static field (frequency-inde­
pendent), isotropic polarizability, 〈α0 〉 exhibits a larger value than
anisotropic polarizability, Δα0 . However, the trend reversed in the
frequency-dependent field. T. Sugino et al. [111] have demonstrated
that the opposite trend is due to different contributing factors in which
(4) 〈α0 〉 increases with the introduction of substituents while Δα is more
affected by the nature of elements and molecular geometry. This ex­
plains the larger 〈α0 〉 in 2F4MA96, which contains two methyl groups,
(5) and the larger Δα in 2F4MA48 due to its higher planarity and
electron-rich thienyl ring. It is also worth noting that the experimentally
determined third-order susceptibility, χ (3) , is directly related to the
anisotropic polarizability, which arises from the reorientation of the
molecule with respect to the field direction [112,113].
The static and dynamic first hyperpolarizabilities of electro-optic
Pockel’s effect (EOPE), β(− ω; ω, 0) and second harmonic generation
(SHG) of first hyperpolarizability, β(− 2ω; ω, ω) are presented in Fig. 15.
βEOPE exhibits a concave decrease with a steep slope, indicating a strong
correlation between β(− ω; ω, 0) response and external frequency.
Meanwhile, apart from the abrupt peaks at 637 and 655 nm, βSHG is
suggested to have a weaker relationship with external frequency, as
opposed to βEOPE . The abrupt peaks of high NLO response, occurring at
wavelengths approximately double of that of the band I absorption
(Table 4), align with the two-state model postulation, associated with
2PA process. This postulation posits that a higher NLO response can be
achieved when the incident wavelength is twice of the maximum ab­
sorption wavelength [114].
The static and dynamic second hyperpolarizabilities of electro-optic
Kerr effect (DC-Kerr), γ( − ω; ω, 0, 0), and electric field-induced second
harmonic generation (EFSHG), γ( − 2ω; ω, ω, 0), are depicted in
14
N.A. Mohamad Daud et al.
Fig. 15. The projection of first hyperpolarizability on dipole moment (βvec ) of 2F4MA48 and 2F4MA96 for (a) electron-optic Pockels effects (EOPE) β(− ω; ω, 0) and
(b) second harmonic generation (SHG) β(− 2ω; ω, ω) with the static hyperpolarizability β(0; 0, 0). Some of βvec (− 2ω; ω, ω) values are negative due to the deviation of
the total hyperpolarizability away from the dipole moment and are omitted in the graph for clarity.
Fig. 16. For electro-optic effects, γKerr response displays values ranging
from 17.21 × 10− 35 to 150.47 × 10− 35 esu, which are found to be
weaker than βEOPE with values ranging from 26.60− 30 to 129.77 × 10− 30
esu, as predicted [115]. Similar to βSHG , another process related to
second harmonic generation, the abrupt peaks of γEFSHG are also asso­
ciated with 2PA process. For comparison with experimentally obtained
parameters, the intensity dependent refractive index (IDRI),
γ( − ω; ω, ω, − ω) and third harmonic generation (THG), γ( − 3ω; ω, ω,
ω) are calculated, utilizing static second hyperpolarizability, γ0 and
electro-optic Kerr effect, γKerr . The relations are given by Eqs. (6) and (7)
[116,117]:
〈γ( − ω; ω, ω, − ω)〉 ≅ 2〈γ( − ω; ω, 0, 0)〉 − 〈γ(0; 0, 0, 0)〉
〈γ( − 3ω; ω, ω, − ω)〉 ≅ 6〈γ( − ω; ω, 0, 0)〉 − 5〈γ(0; 0, 0, 0)〉
The calculated dynamic γ values at 532 nm are 26.50 × 10
IDRI
esu − 34
for 2F4MA48 and 25.27 × 10− 34 esu for 2F4MA96 using B3LYP func­
tional. In CAM-B3LYP, the values are 8.79 × 10− 34 esu (2F4MA48) and
8.56 × 10− 34 esu (2F4MA96). These computed values are considerably
smaller than the experimental values, which are 3.98 × 10− 27 esu for
2F4MA48 and 0.53 × 10− 27 esu for 2F4MA96. Despite the difference in
magnitude, the trend remains consistent in which 2F4MA48 shows a
better NLO response than 2F4MA96. However, it is worth noting that
the larger γ obtained from Z-scan experiment may be influenced by
environmental factors contributing to NLO response, such as thermal
effects or sample purity [118]. Nonetheless, it is further supported
through DFT-estimated (hyper)polarizabilities, the superiority of
2F4MA48 in term of optical nonlinearity as opposed to 2F4MA96.
4. Conclusion
Two fluoro-methoxy substituted chalcone derivatives with different
cinnamoyl systems; methylthienyl (2F4MA48) and dimethylphenyl
(2F4MA96) were synthesized to study the impact of homocyclic and
heterocyclic rings on photophysical responses. These compounds are in
donor-acceptor-donor (D-A-D) configuration, as indicated by the elec­
trostatic potential (ESP) maps. The band I absorption peak of 2F4MA48
occurred at 351 nm, slightly redshifted compared to 2F4MA96 at 329
nm. Interfragmentary charge transfer (IFCT) analysis revealed that band
I is associated with the cinnamoyl system in both compounds. The op­
tical energy gap (Eg) is estimated to be 3.21 eV (2F4MA48) and 3.42 eV
Chemical Physics Impact 8 (2024) 100565
(2F4MA96) using Tauc’s plot method. Consistent with the smaller Eg,
2F4MA48 demonstrated greater optical nonlinearity in terms of
nonlinear absorption (NLA), nonlinear refraction (NLR) and optical
limiting responses. In both compounds, NLA responses are primarily
contributed by genuine 2PA process. The greater optical nonlinearity
response of 2F4MA48 is further supported by density functional theory
(DFT) studies. The theoretical analysis, based on ESP, ELF-π, and FMOs
analyses, revealed that the incorporation of a thienyl ring in 2F4MA48
resulted in greater polarity, an enhanced push-pull effect, lower
aromaticity, a higher degree of electron delocalization, and a smaller
HOMO-LUMO energy gap compared to 2F4MA96, which incorporates a
phenyl ring. The third-order NLO susceptibility (χ (3) ) is determined to be
(6) 8.04 × 10− 8 esu for 2F4MA48 and 1.08 × 10− 8 esu for 2F4MA96. The
second hyperpolarizability (γ) is calculated as 3.98 × 10− 27 esu and 0.53
(7) × 10− 27 esu for 2F4MA48 and 2F4MA96, respectively. The onset
limiting threshold (FS) for 2F4MA48 and 2F4MA96 is 2.63 and 5.32 kJ
cm− 2, respectively while the optical limiting threshold is 5.23 and 5.55
kJ cm− 2, respectively.
CRediT authorship contribution statement
Nur Aisyah Mohamad Daud: Writing – original draft, Visualization,
Software, Methodology, Data curation, Conceptualization. Qin Ai
Wong: Writing – review & editing, Validation, Methodology, Concep­
tualization. Bi Sheng Ooi: Methodology, Data curation. Ching Kheng
Quah: Writing – review & editing, Validation, Supervision, Software,
Resources, Project administration, Funding acquisition, Conceptualiza­
tion. Farah Diana Ramzi: Methodology, Data curation. Yip-Foo Win:
Resources. Parutagouda Shankaragouda Patil: Resources.
Declaration of competing interest
The authors declare the following financial interests/personal re­
lationships which may be considered as potential competing interests:
Quah Ching Kheng reports financial support was provided by Min­
istry of Higher Education Malaysia for Fundamental Research Grant
Scheme (FRGS) with Project Code: Ref: FRGS/1/2023/STG07/USM/02/
4.
15
N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

Fig. 16. Average of cubic hyperpolarizability 〈γ〉 of 2F4MA48 and 2F4MA96 for (a) electro-optic Kerr effect (DC-Kerr) γ( − ω; ω, 0, 0), (b) electric field-induced
second harmonic generation (EFSHG) γ( − 2ω; ω, ω, 0), (c) third-harmonic generation (THG) γ( − 3ω; ω, ω, ω) and (d) intensity-dependent refractive index
(IDRI) γ( − ω; ω, ω, − ω), with the static cubic hyperpolarizability γ(0; 0, 0, 0). Some of γ( − 2ω; ω, ω, 0), values are negative due the direction away from dipole
moment and are omitted in the graph for clarity.

Data Availability Acknowledgements

Data will be made available on request. The authors thank Ministry of Higher Education Malaysia for
Fundamental Research Grant Scheme (FRGS) with Project Code: Ref:
FRGS/1/2023/STG07/USM/02/4 to conduct this work. The authors
also thank Universiti Sains Malaysia (USM) for the research facilities.

Supplementary materials

Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.chphi.2024.100565.

Appendix

A.1 Sheik Bahae formalism of Z-scan experiment

To determine the third-order nonlinear optical parameters, the open-aperture (OA) and closed-aperture (CA) Z-scan data are fitted to Sheik Bahae
formalism [119], following Eq.s A.1 and A.2, respectively:

16
N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

α2 I0 Leff
TOA = 1 − [( )2 ] (A.1)
3
z
zR
+ 1 (2)2

( )
4Δϕ0 zzR
TCA = 1 + [( ) 2 ][( )
2
] (A.2)
z z
zR
+ 9 zR
+ 1

2P 2 1 α0 l )
where TOA (TCA ) is the normalized transmittance of OA (CA) Z-scan data, I0 = πω 2 is the focus intensity in W/cm , Leff = α (1 − e
0
−
is the effective
0
πω20
length of the sample, zR = λ is the Rayleigh range, z is the distance between the sample and the focus, α0 is the linear absorption coefficient of the
sample in cm− 1, l is the sample length, ω0 is the beam waist radius at the focus, λ is the wavelength of incident laser and Δϕ0 is the one-axis phase shift
at the focus.
Through Eq. A.1, nonlinear absorption (NLA) coefficient, α2 (in cm2W− 1) is directly extracted. Meanwhile, through Eq. A.2, Δϕ0 is determined and
subsequently, nonlinear refraction (NLR) coefficient, n2 is calculated using Eq. A.3:
( )( )
λ Δϕ0 ( )
n2 = in cm2 W − 1 (A.3)
2π I0 Leff

With α2 value, the absorption cross section of two-photon absorption (2PA) process is determined by using Eq. A.4:
( )
hν
σ2 = α2 (in GM) (A.4)
NC

where hν is the energy of the excited photon in Joules, NC = NAC is the molecular number density in unit volume, NA is Avogadro’s number and C is the
concentration of the sample solution. (1 GM is 10− 50 cm4s photon− 1)
To determine the excited-state absorption cross-section, σex (in cm2), OA Z-scan data is fitted to Eq. A.5:
⎡ ⎤ ⎡ ⎤
/
⎢ x0 ⎥ ⎢ x0 ⎥
⎢ ⎥ ⎢ ⎥
TOA = ln⎢1 + ( )2 ⎥ ⎢ ( )2 ⎥ (A.5)
⎣ ⎦ ⎣ ⎦
1 + zzR 1 + zzR

0 F0 Leff
where x0 = σex α2h ν , F0 is the on-axis fluence at focus.
Then, for ground-state absorption cross-section, σg , the calculation is conducted following Eq. A.6:
α ( )
σ g = 0 in cm2 (A.6)
NC

Using n2 value, the thermal-optical coefficient, dT

dn
(in K− 1 ) is calculated with Eq. A.7 to compare the significance of thermal lensing in the sample:
( )( ) ( )( )
dn I α0 τ dn α0 ω20
n2 = = (A.7)
dT ρc dT 4κ

where I is the incident intensity, ρ is the sample density, c is the specific heat capacity, τ is the thermal relaxation time, and κ = 0.184 Wm− 1 K− 1 is the
thermal conductivity of DMF (solvent used for Z-scan experiment) at room temperature.
The α2 and n2 values are further used to determine the real and imaginary parts of third-order susceptibility (ℜ(χ (3) ) and ℑ(χ (3) )) using Eqs. A.8 and
A.9, respectively:
(( )( ) 4ε0 cn20 ( )
ℜ χ (3) ( − ω; ω, ω, − ω) in m2 V − 2 = 10− 4 n2 in cm2 W − 1 (A.8)
3
( )( ) 2ε0 c2 n20 ( )
ℑ χ (3) ( − ω; ω, ω, − ω) in m2 V − 2 = 10− 2 α2 in cm W − 1 (A.9)
3ω

where ε0 is the permittivity of free space, c is the speed of light, n0 = 1.4305 is the linear refractive index of DMF at room temperature, and ω = 2λπc is
the angular frequency of light field.
Since the calculated real and imaginary parts of χ (3) are in SI unit (m2 V− 2), unit conversion is conducted from SI unit to gaussian unit (esu)
following Eq. A.10:
( ) 4π
χ (3) in m2 V − 2
=( )2 χ
(3)
(in esu) (A.10)
3 × 104

B. Static and dynamic (hyper)polarizabilities [19]

Taylor expansion of energy if a system in terms of external electric field, F is given as relation B.1.

17
N.A. Mohamad Daud et al. Chemical Physics Impact 8 (2024) 100565

∑ 1 ∑∑ 1 ∑∑∑ 1 ∑∑∑∑
E(F) = E(0) − μi F i − αij Fi Fj − β Fi Fj Fk − γ Fi Fj Fk Fl − …, i, j, k, l = {x, y, z} (B.1)
i
2! i j 3! i j k ijk 4! i j k l ijkl

Where μi , αij , βijk , and γijkl are tensor components of dipole moment, polarizability, first and second hyperpolarizabilities.
The magnitude of electric dipole moment is given by relation B.2
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
|μ| = μ2x + μ2y + μ2z (B.2)

The isotropic and anisotropic polarizability are following relations B.3 and B.4, respectively.
1( )
〈α〉 = αxx + αyy + αzz (B.3)
3
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
( )̅
1 ( )2 ( )2
Δα = √̅̅̅ αxx − αyy + αyy − αzz + (αzz − αxx )2 + 6 α2xy + α2yz + α2xz (B.4)
2
The magnitude of first hyperpolarizability, β and the projection on dipole moment vector are given by relations B.5 and B.6, respectively:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
|β| = β2x + β2y + β2z (B.5)

∑μ βi
βvec = i
(B.6)
i
|μ|

Where βi (i = x, y, z) is given by equation B.7,

1 ∑( )
βi = β + βjij + βjji (B.7)
3 j=x,y,z ijj

The averaged isotropic second hyperpolarizability, 〈γ〉 is following relation B.8:

1[ ( )]
〈γ〉 = γ + γyyyy + γ zzzz + 2 γ xxyy + γxxzz + γ yyzz (B.8)
5 xxxx

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