Effect of nonlinear optical (NLO) properties featuring donor-π-donor chromophores in the

extended localised π-conjugation diformyltriphenylamine disubstituted chalcone derivatives

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Nurul Nabilah Shuaib1, Adibah Izzati Daud1,*, Suhana Arshad2, Mohamad Aizat Abu Bakar3,
Norazlan Mohmad Misnan4
1Faculty of Chemical Engineering & Technology, Universiti Malaysia Perlis, 02100 Padang

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Besar, Perlis, Malaysia.
2School of Physics, Universiti Sains Malaysia, 11800 USM, Pulau Pinang, Malaysia.
3Institute of Nano Optoelectronics Research and Technology (INOR), Universiti Sains Malaysia,
11800 USM, Penang, Malaysia.

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4Herbal Medicine Research Centre, Institute for Medical Research, National Institutes of Health,

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Shah Alam 40170, Selangor, Malaysia

*Corresponding author: adizzati@unimap.edu.my

ABSTRACT
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This study investigates the influence of substituent groups featuring different electron-donating
strength on the nonlinear optical (NLO) properties of four novel chalcone derivatives (DFC1 –
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DFC4), combining experimental and theoretical approaches. Spectroscopic characterization was
conducted via FT-IR and NMR, while thermal stability was assessed through TGA. Linear and
third-order NLO behaviours were determined using a UV–Vis spectrometer and a Z-scan technique
with 532 nm excitation. Theoretical analysis through density functional theory (DFT) and time-
dependent DFT (TDDFT) with B3LYP functionals supported experimental findings, focusing on
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geometry optimization, global reactivity descriptors, and photophysical properties including

HOMO-LUMO energy levels. NLO properties, including dipole moment, polarizability, and
hyperpolarizabilities, were calculated using a numerically differentiated analytic method. Z-scan
data revealed that DFC1 – DFC4 NLO responses, significantly affected by electron-donating
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groups and intermolecular interactions, position them as promising materials for optoelectronic and
NLO applications.

Keywords: D-π-D chalcone derivatives, nonlinear optical properties, third-order NLO, extended π-
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conjugation, Z-scan analysis

1. Introduction
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Currently, the introduction of laser technology has flourished the exploitation of nonlinear optical
(NLO) response materials, especially in the optical field, which has been derived from second-order
phenomena of frequency conversion [1] as well as third-order phenomena, including non-linear
refraction (NLR) and non-linear absorption (NLA). In addition, the incorporation of organic
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materials with excellent two-photon absorption mechanisms attributed by reverse saturable

absorption (RSA) characteristics, is in high demand because of their versatile applications in
photonic and optoelectronic fields [2]. The rapid advancement in NLO materials opens a plethora

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 of promising fields for materials engineers to fabricate new devices for various related
optoelectronic applications such as organic light emitting diode [3,4], molecular switching [5], and

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molecular photonics [6]. Due to these impressive applications of NLO materials have attracted
material scientists to design and develop new materials possessing high nonlinear absorption
coefficient (β), large molecular hyperpolarizability (γ), and third-order nonlinear optical
susceptibility (χ3).

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There is a large interest in studying organic NLO molecules having extended localized π-conjugated
systems as they possess larger NLO coefficients with a vast number of design possibilities. The
enormous amount of work that has been carried out in this area reported that organic molecules
especially the one with chalcone molecular backbone exhibit large second and third-order NLO
behavior with high intensity of laser pulse. Previously, the past few years have reported an increase
in the application of chalcone (known as α, β-unsaturated ketones) derivatives in the biological and

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pharmacological field [7,8]. Despite their biological importance, recent years have seen the
successful development of NLO characteristics of chalcone derivatives with appropriate

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chromophores substitutions have been explored for many years for their various application in
optoelectronic and molecular switching devices [9,10].

The underlying factors driving chalcone derivatives that have attracted significant attention in
developing NLO materials mainly because of their availability in edible plants [11], structural
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flexibility [12], easy-synthesizable materials and high optical nonlinearities due to the significant
delocalization of the electronic cloud with the chalcone molecular framework. Additionally, the
presence of carbonyl group functionalities in conjugation with the adjacent donor/acceptor
chromophores provided the charge-transferring bridge that made chalcone derivatives exceptional
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candidates for NLO-related applications [13,14]. Examples of chalcone derivatives such as pyrenyl,
phenyl, heterocyclic, and anthracene-based chalcone are among a group of organic materials that
exhibit 2nd and 3rd-order nonlinearity. The structure of chalcone derivatives can be altered to
investigate their structure-property relationship and to enhance the nonlinearity of the compound.
From the literature, several recent approaches highlighted that the results from excellent optical
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nonlinearity of the chalcone derivatives are due to the π-electron conjugated system, which affords
intramolecular charge transfer (ICT) throughout the molecules, which alternately decreases the
energy band gap of the compounds. Research has demonstrated that various factors such as donor-
acceptor strength substitution, the arrangement of substituents, the extent of conjugation,
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intermolecular interactions, molecular planarity, and conformation play a substantial role in

influencing the performance of nonlinear optical properties (NLO) [15–17]. To gain a
comprehensive understanding of how substituents impact these nonlinearities, it is essential to
conduct a complementary study incorporating both theoretical and experimental perspectives.
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The Quantum computational method is a part of theoretical investigation, especially density

functional theory (DFT) has shown to be highly successful in describing the structural and electronic
properties of a diverse class of materials. DFT has been known for decades to be the simplest and
easiest method to understand the physiochemical properties of the synthesized molecular system
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[18]. The NLO parameters can be easily computed using the DFT methods for suitably varied
structures. DFT has emerged as an excellent tool among materials characterization techniques to
identify the vibrational properties, intermolecular interactions, electron density distribution, and
nonlinear optical characteristics [19].
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 In continuation of our interest to explore NLO characteristics of chalcone derivatives, a part of
exploring D-π-A functionalities in NLO, we have synthesized and investigated the D-π-D molecular

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structure (FT-IR, NMR), thermal properties (TGA), linear optical (UV-Vis) and 3rd order nonlinear
optical properties of disubstituted chalcone derivatives (DFC1-DFC4) with extended π-
conjugation, featuring diformyltriphenylamine as a π-linker have been investigated. The 3rd order
NLO characteristic of DFC1-DFC4 were carried out in solution phase with 0.01 M samples
concentration via open- and close-aperture Z-scan analysis under continuous wave (CW) laser

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excitation, which concerns the dependence of the transmission on the movement of the sample along
z-position. This method includes the information about non-linear absorption coefficient (α2) and
nonlinear refractive index coefficient (n2), which are both related to the complex of 3rd-order
susceptibility χ3. In addition, DFT calculation has been carried out to draw insights into the
structural and electronic properties. To account for the NLO purposes, the detailed analysis of
molecular electrostatic potential (MEP), HOMO-LUMO energy band gap, global chemical

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reactivity descriptors (GCRD), dipole moment, and hyperpolarizability were calculated via DFT
method to describe the correlation between the donor chromophores substitution in the D-π-D

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system with their optical nonlinearity.

2. Experimental procedure

2.1.
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Synthesis of disubstituted diformyltriphenylamine chalcone derivatives (DFC1-DFC4)

All reactants and solvents in the analytical grade were used as received without further purification
and were purchased from Merck, Malaysia. The disubstituted diformyltriphenylamine chalcone
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derivatives (DFC1-DFC4) were synthesized according to the Claisen-Schmidt reaction [20].
DFC1, DFC2, DFC3, and DFC4 having anthracene, pyrene, 3,5-bis-trifluoromethyl, and 3-acetyl-
5-methyl-furan as the anchoring chromophore groups were synthesized by the condensation
reaction between appropriately substituted acetophenone (2 mmol) with 4,4′-
diformyltriphenylamine (1 mmol) in absolute ethanol (70 mL) in the presence of a catalytic amount
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of 10% sodium hydroxide (NaOH) solution. The reactants were vigorously stirred for
approximately 5 hours until the formation of a precipitate. Once the reaction was completed, the
reaction mixture was poured into ice blocks and the mixture was left overnight. The obtained
precipitate was filtered, washed with ice water, and dried in a container containing silica gel. The
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obtained crude product was subjected to recrystallization from acetonitrile to obtain the
corresponding title compounds with a good percentage (%) yield. Scheme 1 indicates the reaction
route to the synthesis of disubstituted diformyltriphenylamine chalcone derivatives (DFC1-DFC4).
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 O O O

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O O
R CH3 + H H EtOH, NaOH
R R
N
Room temperature N

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F3C
R= O
H3C

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CF3

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Scheme 1. DFC4 The reaction
DFC1 DFC2 DFC3
route to the synthesis of
DFC1-DFC4.
2.2. Spectroscopic analysis
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DFC1-DFC4 were spectroscopically investigated using the potassium bromide (KBr) pellet method
on a Perkin Elmer Fourier-transform infrared (FT-IR), in the frequency range 4000-400 cm-1. The
1H and 13C Nuclear Magnetic Resonance (NMR) spectra were recorded in CDCl using Bruker
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Avance III 400 Spectrometer in the range δH 0–15 ppm and δC 0–200 ppm accordingly regarding
the trimethylsilane (TMS) as internal standard at ambient temperature. The linear absorption
spectrum of DFC1-DFC4 in acetonitrile at a concentration of 1 x 10-5 M was recorded using a
Perkin Elmer UV-Vis spectrophotometer in the wavelength region 200 – 900 nm. The thermal
characteristics of the synthesized compounds, DFC1-DFC4, were studied by thermogravimetric
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analysis on a Perkin Elmer TGA analyzer within the temperature range 30-900 °C at the heating
rate of 10 C°/min.
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2.3. Z-scan analysis

The z-scan method is one of the most effective tools used to investigate the nonlinear optical
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behavior of synthesized compounds. The third-order nonlinear optical properties of DFC1-DFC4

were carried out via both open- and close-aperture Z-scan technique. The schematic representation
of the Z-scan analysis for the third-order NLO investigation is shown in Fig.1 [21]. The samples of
0.01 M concentration in acetone were scanned along the Z-direction. Through Z-scan analysis, there
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are two quantitative phenomena occurred, which are nonlinear reflection (NLR) and nonlinear
absorption (NLA). This method also provides information on the sign of optical nonlinearity,
nonlinear absorption coefficient (β), nonlinear refractive index (n2), third-order susceptibility (χ3),
and the type of nonlinearity possessed by each of the synthesized DFC1-DFC4. A CW diode-
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pumped solid-state laser was implemented as a light source, operating at 532 nm wavelength (λ)
with 200 mW output power. The obtained data were analyzed using the Z-scan theory as reported
in [22]. To calculate the effective nonlinear absorption (βeff) value, the normalized transmittance
was plotted according to Lavenberg-Marquardt algorithm through equation Eq. (1):

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 ed
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Fig.1. Schematic diagram of Z-scan analysis for third-order NLO investigation [21].
∞ [ ― 𝑞0(𝑧)]𝑚
𝑇(𝑧, 𝑠 = 1) = ∑𝑚=0
(𝑚 + 1)3 2

Eq. (1) er
𝛽𝐼0𝐿𝑒𝑓𝑓
2
where 𝑞0(𝑧) =
( 𝑧2
) , 𝑧𝑅 = 𝑘𝜔0 is the diffraction length of the beam and 𝜔0 is the beam
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1+
𝑧 𝑅2 2
waist radius at the focal point and 𝑘 = 2𝜋 𝜆 is the wave vector. In addition, to obtain more details
about the origin of the nonlinearity absorption (NLA), the ground (σg) and excited (σex) state
absorption cross-sections were discussed. The value for σg can be calculated as in equation Eq. (2):
𝛼
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𝜎𝑔 = 𝑁 𝐴𝐶 Eq. (2)

where α is the linear absorption coefficient of the sample, Na is Avogadro’s number, and C is the
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solution concentration, while the σex can be found by fitting the OA data according to the following
equation Eq. (3):
2ℎ𝑣𝑞𝑜
𝜎𝑒𝑥 = 𝛼𝐹𝑜𝐿𝑒𝑓𝑓 Eq. (3)
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where Fo is the laser fluence at the focus point and hv is the incident photon energy. The close
aperture data is fitted theoretically to investigate the nonlinear optical reflection effect, NLR,
using the following equation Eq. (4):
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(4𝑋∆𝜗𝑜)
𝑇 (𝑍) = [1 ― (𝑋2 + 1)(𝑋2 + 9)]
Eq. (4)
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Where X = Z / Zo, ∆𝜗𝑜= kn2IoLeff and wave vector k = 2π/λ. The outcome of βeff and n2 is used to
compute the components of the third-order nonlinear optical susceptibility (χ3) via the following
equations, Eq. (5) – Eq. (7).

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 Re 𝜒(3)(𝑒𝑠𝑢) = 10―4
𝜀0𝑐2𝑛02
𝜋
𝑛2 (𝑐𝑚𝑊 )
2
Eq. (5)

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𝜀0𝑐2𝑛02𝜆
Im 𝜒(3)(𝑒𝑠𝑢) = 10―2 4𝜋2
𝛽 (𝑐𝑚
𝑊
) Eq. (6)

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𝑙𝜒3𝑙 = (𝑅𝑒(𝜒3))2 + (𝐼𝑚(𝜒3))2 Eq. (7)

where 𝜀0 is the permittivity of free space.

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2.4. Computational analysis
Quantum chemical calculation and ab initio method have attracted high interest among researchers
because of substantial advancements in computational study. Particularly, for the structural
elucidation involving organic compounds, density functional theory (DFT) approaches based on
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B3LYP method have proven to produce results with high accuracy [23]. The complete DFT
calculation was performed by DFT with B3LYP / 6-31G (d, p) via Gaussian 09W program package,
while the images, graphs, and data analysis were visualized using Gauss View 5.0 visualization
program. The molecular structure of DFC1-DFC4 were optimized to ground state energy with basic
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set of B3LYP / 6-31G (d, p) level of theory, and the optimized geometric molecular structures were
used for further calculations. Furthermore, the theoretical electronic excitation energies including
frontier molecular orbital analysis, absorption wavelengths, and oscillator strength of DFC1-DFC4
were calculated at theoretical levels of time-dependent density functional theory (TD-DFT) B3LYP
/ 6-31G (d, p). Various parameters were calculated consist of HOMO-LUMO energies, excitation
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energies, molecular electrostatic potentials, and global chemical reactivity descriptors (GCRD). The
nonlinear optical properties such as static dipole moments (µ), mean polarizability (<α>), anisotropy
polarizability (∆α), first hyperpolarizability (β), and average second hyperpolarizability (<γ>) were
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successfully computed via B3LYP / 6-31G (d, p) level of theory under finite field scheme at ω = 0,
and the values obtained were calculated using the following equations, Eq. (8) – Eq. (11) [24].

1/2
µ𝑡𝑜𝑡 = (µ2𝑥 + µ2𝑦 + µ2𝑧 )
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Eq. (8)

1
< 𝛼 >= 3
(𝛼𝑥𝑥 + 𝛼𝑦𝑦 + 𝛼𝑧𝑧) Eq. (9)
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1 1/2
∆𝛼 = √2
[(𝛼𝑥𝑥 ― 𝛼𝑦𝑦)2 + (𝛼𝑦𝑦 ― 𝛼𝑧𝑧)2 + (𝛼𝑧𝑧 ― 𝛼𝑥𝑥)2 +6(𝛼2𝑥𝑦 + 𝛼2𝑥𝑧 + 𝛼2𝑦𝑧)] Eq. (10)

1
< 𝛾 > = 5[𝛾𝑥𝑥𝑥𝑥 + 𝛾𝑦𝑦𝑦𝑦 + 𝛾𝑧𝑧𝑧𝑧 +2(𝛾𝑥𝑥𝑦𝑦 + 𝛾𝑥𝑥𝑧𝑧 + 𝛾𝑦𝑦𝑧𝑧)] Eq. (11)
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 3. Result and Discussion
3.1. FT-IR vibration analysis

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The Fourier Transform Infrared (FT-IR) spectra of chalcone derivatives DFC1-DFC4 are
characterized by four primary vibrational modes corresponding to the C=C (aromatic), C=O, C-N,
and CH2 groups. The carbonyl (C=O) group, located in the ethylenic bridge, is crucial for charge

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transfer, with its ν(C=O) stretching modes presenting as strong, sharp peaks in the 1640 – 1690 cm-1
range. This heightened intensity of the C=O peak results from the disparity in the electronegativities
of carbon and oxygen, leading to an unequal electron distribution in the bond. The ν(C=O) peak
exhibits a redshift relative to the standard ν(C=O, 1700 cm-1) due to π-electron conjugation with
the α and β carbons of the ethylene in the enone linkage, reducing the C=O bond order [16,25].
Additionally, the C=C stretching vibration is observed between 1582 – 1588 cm-1. Peaks in the 3027

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– 3048 cm-1 range are attributed to the C-H (aromatic) stretching mode. The presence of
diformyltriphenylamine in the derivatives is indicated by strong C-N stretching vibrations,

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appearing in the 1169 – 1178 cm-1 spectrum. Fig. 2 shows FT-IR spectrums of DFC1 – DFC4.

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Fig. 2. The FTIR spectrum of chalcone derivatives, DFC1 – DFC4.

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 3.2. Nuclear Magnetic Resonance (NMR)
In 1H-NMR analysis, diformyltriphenylamine disubstituted chalcone derivatives (DFC1 – DFC4)

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exhibited primary aromatic resonances within δH 6.17 – 8.42 ppm, reflecting triphenylamine
structures. DFC1 (anthracene) resonated at δH 7.26 – 8.52 ppm, DFC2 (pyrene) at δH 7.32 – 7.60
ppm, DFC3 (furan) at δH 7.48 – 7.54 ppm, and DFC4 for aromatic signals appeared at δH 6.64 –
6.90 ppm. DFC3 for methyl protons were noted at δH 2.39 ppm. Chalcone α and β protons in DFC1

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– DFC4 were identified at δH 7.21 – 8.05 ppm, with a 4Hz coupling constant, indicating π-electron
delocalization effects linked to the carbonyl group. The 13C-NMR data corroborated these findings,
with significant carbon signals ranging from 109.1 – 158.19 ppm across derivatives, highlighting
the aromatic carbons. Vinyl carbon signals were distinguished at 149.5 – 177.3 ppm, and the
carbonyl carbons confirmed chalcone structures at 183.2 – 195.7 ppm.

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3.3. Electronic transition studies

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Linear absorption and electronic transition studies of DFC1-DFC4, conducted in the 200 – 800 nm
wavelength range, revealed distinct absorption characteristics. DFC1-DFC3 displayed two bands
indicative of different electronic transitions, whereas DFC4 showed a singular band. The absorption
maxima for DFC1-DFC4 were observed at 252 nm (DFC1), 241 nm (DFC2), 222 nm (DFC3), and
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307 nm (DFC4), corresponding to π→π* transitions. A second set of bands for DFC1-DFC3,
observed at 335 nm, 433 nm, and 288 nm, represented overlapping π→π* and n→π* transitions.
The π→π* transitions are linked to conjugated aromatic chromophores, while n→π* transitions
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arise from nonbonding electrons in nitrogen and oxygen atoms. Notably, DFC1 and DFC2, with
stronger donor substituents (anthracene and pyrene, respectively), exhibited bathochromic shifts,
while DFC3 (methyl furan) and DFC4 (trifluoromethyl), with weaker donor properties, showed
hypsochromic shifts. Fig. 3 illustrates the UV-visible spectra of DFC1-DFC4.
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Fig. 3. UV-Visible spectra of DFC1-DFC4.

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 3.3.1. TD-DFT
The TDDFT absorption peaks are simulated in the acetonitrile solvent employing IEFPCM model

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to investigate the phenomenal impact of incorporated various donors group on the spectral
characteristic such as electronic transition, electronic configuration, and charge transfer possibilities
of the synthesised chromophores. Conjugation and donors substitution effect from the molecules
impart a large bathochromic shift in UV-Vis absorption spectra [26]. The calculated TD-DFT

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spectra of our designed compounds with D-π-D (DFC1-DFC4) configuration is shown in Fig. 4.
The excitation energy, absorption maxima, oscillator strength, and molecular orbitals contributions
are tabulated in Table 1. All the simulated molecules DFC1-DFC4 exhibit absorption maxima in
the visible wavelength, in which all the calculated λmax of all the molecules is found in the range
487 – 519 nm. DFC1 has a largest maximum absorption wavelength of 519 nm, 2.38 eV transition
energy, and a molecular orbitals contribution of 91% transition occurred from HOMO→LUMO.

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This enlarged absorption wavelength attributed by the presence of pyrene as a donor moiety

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indicating efficient resonance effect from the rings. DFC2 shows a maximum λmax value of 517 nm,
transition energy of 2.39 eV, oscillator strength of 1.17, and 95% molecular orbitals contribution
from HOMO→LUMO. DFC3 has a slightly blue shifted absorption maxima at 487 nm with
transition taking place at 2.54 eV or energy, an oscillator strength of 1.20, and 99% molecular
orbitals contribution from HOMO→LUMO. DFC3 experience a blue shifted absorption maxima
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due to the presence of furan as poor electron donor moiety, with less electron conjugation inside
furan. DFC4 exhibits absorption maxima at 518 nm with 2.39 eV transition energy taking place,
1.12 oscillator strength and 99% molecular orbitals contribution from HOMO→LUMO. The
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occurrence of significant red shifted absorption spectrum in DFC4 indicating the efficiency of
utilized donor moieties though the CF3 considered as weak electron donor compared to anthracene
(DFC1) and pyrene (DFC2). Interestingly, all the tailored compounds except DFC3 possess large
absorption wavelengths due to the factors influenced by the presence of resonating electron-rich-
donor moieties that enable extensive conjugation in the designed compounds. However, the
theoretical obtained λmax gave a different λmax to the experimentally predetermined absorption
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maxima [27]. This is because, experimental data might be affected by intermolecular charge transfer
between the molecules and the solvents which gave slightly different either red or blue shifted λmax.
In addition, the efficiency of light absorption in all the synthesised compounds can be investigated
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by a significant factor known as the light harvesting efficiency (LHE) obtained from TD-DFT
calculations. Theoretically, molecules with higher LHE values possess excellent response in term
of generating photocurrent. The LHE values can be calculated using Eq. (13) and the results
tabulated in Table 1.
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𝐿𝐻𝐸 = 1 ― 10―𝑓 Eq. (13)

In the given equation, f represents the oscillator strength. The LHE values of all the synthesised
compounds are found to be very similar to each other with DFC3 found to exhibit the highest LHE
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value among the studied compounds given preliminary indicator that DFC3 has ability to generate
photocurrent.
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 ed
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Fig. 4. TD-DFT spectra of calculated DFC1 – DFC4.
Table 1. The excitation energy, absorption maxima, oscillator strength, light harvesting efficiency
(LHE), and molecular orbitals contributions of DFC1-DFC4.
Compounds λmax (nm) E (eV) fosc LHE MO contributions
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DFC1 519 2.38 1.09 0.9187 H→L (91%)

DFC2 517 2.39 1.17 0.9323 H→L (95%)
DFC3 487 2.54 1.20 0.9369 H→L (99%)
DFC4 518 2.39 1.12 0.9241 H→L (99%)
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f=oscillator strength, MO=molecular orbital H=HOMO, L=LUMO

3.2.2. Optical energy band gap (Egap): Tauc plot

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The optical band gap (Egap) of every synthesised material is an important parameter in optoelectronic
field to determine material’s atom structure, electronic band structure as well as electro-optic
properties of the material. The dependence of the absorption coefficient as a function of photon
energy is useful to study band structure and electronic transition. The optical absorption coefficient
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(α) can be obtained using Eq. (14),

𝛼 = 2.303 𝑥 𝐴/𝑡 Eq. (14)
where t is the thickness and A is the absorbance of the sample. The optical band gap (Egap) of DFC1-
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DFC4 can be calculated from the UV-vis absorption spectra in which the optical absorption
coefficient (α) is given by Tauc’s relation in Eq. (15),

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 (𝛼ℎ𝑣) = 𝐴(ℎ𝑣 ― 𝐸𝑔𝑎𝑝)1/2 Eq. (15)

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where h is Planck’s constant and v is the frequency of incident photons. The band gap of DFC1-
DFC4 materials is obtained as the energy difference between the HOMO and LUMO by
extrapolating the linear (ahv)2 vs E (eV) until it intersects the E axis as shown in Fig. 5. DFC1 and

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DFC2 with anthracene and pyrene substitution exhibited the smaller values of optical band gap
(Egap) demonstrating the influence of donor substitution in lowering the band gap of materials [28].
Conversely, in the compound of DFC3 and DFC4 with methyl furan and trifluoromethyl
substitution exhibited larger values of optical band gap (Egap). This is since methyl furan and
trifluoromethyl are both from weak electron donor groups that provoke a blue-shift towards higher
energy.

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Fig. 5. Tauc plot for energy band gap (Egap) determination of DFC1-DFC4.
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 3.4. Frontier molecular orbitals (FMOs)
Frontier molecular orbitals (FMOs) is used to obtain insightful characteristic of the intramolecular

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charge transfer due to the electron excitation, the HOMO-LUMO gap energies, dipole moments of
molecules, electron population, and energy changes of donor-acceptor groups as evidence of the
push-pull effect nature of DFC1 – DFC4. The HOMO-LUMO of DFC1-DFC4 clearly exhibited
the π-nature of the molecules. From the molecular orbital isosurfaces of DFC1-DFC4 (Fig. 5), it

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clearly indicated that HOMO is localized on the π-conjugated C=C, C=O, and aromatic ring whereas
the LUMO is observed around triphenylphosphine substitution. As expected, calculated HOMO-
LUMO exhibits different energies provoking important differences of donor-acceptor substitution
in the molecules. In fact, the largest dipole moments are found for compound DFC4 containing CF3
as the strong acceptor. The chromophore with small Egap is found to be highly reactive, less stable,

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and commonly known as soft molecule. Likewise, the narrow Egap indicates significant
intramolecular charge transfer, thus exhibiting higher polarizability and suitable candidate for NLO

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materials. The calculated HOMO-LUMO energy gap is listed in Table 2, while the energy diagram
of DFC1-DFC4 is as illustrated in Fig. 6.

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Table 2. EHOMO, ELUMO, dipole moment, and Egap of DFC1-DFC4.

Compound E (HOMO) E (LUMO) Egap (eV) Dipole moment

DFC1 -5.24 -2.43 2.81 4.6129
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DFC2 -5.25 -2.44 2.81 4.6660
DFC3 -5.45 -2.49 2.96 5.1810
DFC4 -5.33 -2.32 3.01 6.1199
ot
tn
rin
ep
Pr

Fig. 6. Energy diagram of DFC1-DFC4.

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 From Table 2, the EHOMO/ELUMO energies of all the designed chromophores DFC1-DFC4 are -5.24/-
2.43, -5.25/-2.44, -5.45/-2.49, and -5.33/-2.32 eV respectively. The modulate compounds show an

ed
increase in HOMO-LUMO energy gaps (2.81-3.01 eV) due to the presence of different donor
strength functional groups substituted to the molecular backbone of triphenylamine. The
incorporation of fused aromatic substitution (i.e. anthracene (DFC1), pyrene (DFC2)) along with
triphenylamine as π-linker possess energy gap reduction with the lowest energy values. In addition,

iew
the presence of lone pair on nitrogen and oxygen atoms in triphenylamine and furan moieties
induces positive inductive effect along with the resonance effect, in which increasing the availability
of electrons for donating purposes hence entails bulk charge transfer within molecules. Among the
derivatives, DFC4 exhibits the largest Egap (3.01 eV) values as the substitution is 1,3-trifluromethyl
considered as less efficient electron donors as compared to anthracene and pyrene. A narrow energy

v
gap observed in both DFC1 and DFC2 resulted from highly conjugated fused aromatic rings of
anthracene and pyrene making the compounds electron-rich donor moiety which enforcing push-

re
pull channel. DFC3 reveals an Egap of 2.96 eV as the presence of two heteroatoms (N and O) results
in extended conjugation of the donor moiety. Egap has found to decrease in the following manner:
DFC4 > DFC3 > DFC2 = DFC1. This reduction of HOMO/LUMO energy gap trend implies that
the substantial incorporation of strong electron donating substituents on the donor part is a
er
successful method to attain enhanced NLO activity. The charge transmission process is proficiently
described by the surface diagram showing electronic charge density distribution. As illustrated in
Fig.5, it is proven that HOMOs are mostly concentrated over π-linker, whilst LUMO concentration
is dominated more at donor moiety compared to the acceptor moiety, revealing the occurrence of
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intermolecular charge transfer (ICT) in the synthesised compounds [7,29]. These surface diagrams
evidence that charges transfer occurred proficiently in the synthesised chromophores, thus making
them efficient NLO materials.
ot

3.5. Global reactivity molecular descriptors

Egap, EHOMO, and ELUMO were calculated from FMOs are subsequently involved in the computation
of global reactivity molecular descriptors. The parameters include ionization potential (IP), electron
tn

affinity (EA), chemical potential (µ), global hardness (ƞ), electronegativity (χ), global
electrophilicity (ω), and global softness (δ). These parameters are important for numerous chemical
activities. All calculated global reactivity molecular descriptors are tabulated in Table 3. IP is
designated as energy intake upon excitation of electrons from HOMOs, while the energy discharged
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upon incorporating electrons in LUMOs is taken as EA [30]. In other words, the electron-acceptance
and donation aptitudes of analyzed compounds are described by EA and IP values, respectively.
The IPs and EAs of DFC1-DFC4 are 5.24 – 5.45 and 2.32 – 2.49 eV respectively, indicating facile
charge transfer from donor to acceptor moieties. The decreasing trend for the IP values is DFC3
ep

(5.45)>DFC4 (5.33)>DFC2 (5.25)>DFC1 (5.24), while the declining trend for EA is as follows
DFC3 (2.49)>DFC2 (2.44)>DFC1 (2.43)>DFC4 (2.32). In the same manner, the electronic cloud
attraction in the atomic vicinity known as electronegativity. The electronegativity for DFC1-DFC4
is 3.84, 3.85, 3.97, and 3.83 respectively. Chemical potential, encompassing global electrophilicity
Pr

index, softness, and hardness, contributes to the stability, reactivity, and polarizability of
chromophores. Accordingly, chromophores comprising greater magnitudes of hardness and
chemical potential are kinetically stable. While the chromophores having larger magnitudes of
softness parameter are chemically reactive and polarizable [15]. Among the entitled chromophores,

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 DFC1 and DFC2 has the lowest hardness parameter (1.41 eV) and the highest softness parameter
(0.35 eV), anticipating it as the most reactive and polarizable species. Among all the designed

ed
compounds, DFC4 possesses the smallest softness (0.33 eV) and the largest hardness (1.51 eV)
values, making it the most stable and least polarized chromophore. The decreasing order for
hardness values is found as DFC4 (1.51 eV) > DFC3 (1.48 eV) > DFC1 = DFC2 (1.41). The global
softness (σ) values found in the increasing order of DFC4 (0.33 eV) < DFC3 (0.34 eV) < DFC2 =

iew
DFC1 (0.35 eV). Further, global softness and hardness are in complete agreement with the Egap
trend, indicating that small Egap molecules acquire the highest softness with the lowest hardness
values [31]. Intriguingly, all these parameters conclude the remarkable efficacy of the modified
compounds as preferred reactive NLO materials.

Table 3. Global reactivity molecular descriptors of DFC1-DFC4 in eV.

v
Compounds IP EA µ χ ƞ ω δ

re
DFC1 5.24 2.43 -3.84 3.84 1.41 5.23 0.35
DFC2 5.25 2.44 -3.85 3.85 1.41 5.26 0.35
DFC3 5.45 2.49 -3.97 3.97 1.48 5.32 0.34
DFC4 5.33 2.32 er -3.83 3.83 1.51 4.86 0.33

3.6. Thermal Analysis of DFC1-DFC4

Thermal stability of diformyltriphenylamine-substituted chalcone derivatives (DFC1-DFC4) was
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assessed under a nitrogen atmosphere from 30 to 900 ℃, as depicted in Fig. 7. DFC1-DFC3
exhibited two-stage degradation, while DFC4 showed a three-stage pattern. The initial
decomposition, ranging from 231 to 459 ℃, accounted for a weight loss of 13.93-24.56%, attributed
to the breakdown of substituent groups (benzene, methyl furan, trifluoromethyl) and carbonyl
functionalities. The second degradation phase occurred between 309 and 800 ℃, with weight losses
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between 17.12-35.65%. DFC1 emerged as the most thermally stable up to 334 ℃, followed by
DFC2, DFC3, and DFC4, the latter displaying a lower onset temperature likely due to its easily
decomposable trifluoromethyl substituents. No phase transitions were observed below the onset
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temperature, indicating stability against water loss. Residual char accounted for 53.99%, 62.64%,
58.41%, and 30.38% of DFC1, DFC2, DFC3, and DFC4, respectively, with DFC1-DFC3 showing
higher ash content from non-decomposable carbon residues. The thermal decomposition
temperatures of DFC1-DFC4 exceeded 200 ℃, aligning with criteria for optoelectronic device
durability and suitability for nonlinear optical (NLO) applications due to their higher thermal
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decomposition thresholds [32]. Table 4 presents detailed thermogram data analysis.

ep
Pr

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 ed
v iew
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Fig. 7. Thermogram of DFC1-DFC4.
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Table 4. Thermogravimetric analysis (TGA) of DFC1-DFC4.
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Onset Final
Expected moieties
Compound temperature, Weight loss (%) residue
decomposition
Td (ºC) (%)
1st stage: 333.88-397.12 ºC
Benzene/C=O
(24.56%); [Calc: 25.53 %]
DFC1 333.88 53.99
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2nd stage: 397.12-800.05 ºC

anthracene
(21.45%); [Calc: 21.56 %]
1st stage: 326.86-418.67 ºC
Benzene/C=O
(13.93%); [Calc: 13.68 %]
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DFC2 326.86 62.64

2nd stage: 418.67-780.83 ºC
pyrene
(23.43%); [Calc: 23.63C %]
1st stage: 326.10-458.96 ºC
Methyl Furan/C=O/Methyl
(24.47%); [Calc: 26.51 %]
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DFC3 326.10 58.41

2nd stage: 458.96-790.01 ºC
Benzene
(17.12%); [Calc: 18.31 %]
1st stage: 231.65-309.39 ºC
CF3/C=O
(20.23%); [Calc: 21.35 %]
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2nd stage: 309.39-441.86 ºC Trifluoromethyl

DFC4 228.54 30.38
(35.65%); [Calc: 37.06 %] benzene/Benzene
3rd stage: 441.86-764.71 ºC
C=O
(13.74%); [Calc: 13.52 %]
Pr

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 3.7. Z-Scan Analysis

ed
The open and close aperture Z-scan experiment were conducted on DFC1-DFC4 to study the
nonlinear absorption (NLA) and nonlinear refractive index (NLR) properties at a laser output power
of 200 mW and a laser beam wavelength of 532 nm. In this approach, a strong laser beam is
projected through a lens to the cuvette containing the sample. The sample-loaded cuvette is shifted

iew
about the focus region, and changes in the far-field intensity pattern are adjusted. The normalized
transmittance of the sample without aperture was determined in the far field as the sample went past
the focus point, whereas the sample including media exhibits the sign of NLA which can eventually
allow us to determine the NLA coefficient (β) [10]. The open aperture curves of DFC1-DFC4 are
shown in Fig. 8. All curves are symmetric with the respect to the focus (Z=0). The calculated values
of β are listed in Table 5. Based on the theoretical fit for the experimental data of the DFC1-DFC4,

v
the values of β were found to be 5.75 ×10−4, 1.26 ×10−4, 7.59 ×10−4 and 3.05 ×10−4 cmW −1

re
respectively. The obtained open aperture curve revealed a symmetric valley about the focus (Z=0).
This proved that these compounds exhibit two-photon absorption with strong reverse saturation
absorption (RSA) which explained the positive nonlinear coefficient (β).
The peak-valley module in Fig. 9 indicates a negative nonlinear refraction (n2) in closed aperture
er
curve of DFC1-DFC4 due to the self-defocusing effect arising from these compounds. The closed
aperture curve was modelled theoretically with experimental data which gives the value of -1.90
×10−15, 1.27 ×10−15, 3.41 ×10−15 and 2.28 ×10−15 cm2W-1 for DFC1-DFC4 respectively. The
observed asymmetric nature of the curve is due to the thermally induced NLR process since a CW
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laser was used as an excitation source. The presence of a self-defocusing effect in any optical
medium may be advantageous in NLO applications, particularly for photonic and optoelectronic
devices [10]. The obtained value of n2 for DFC1-DFC4 are presented in Table 5.
The nonlinear optical susceptibility (χ3) determined the efficacy of NLO activity of a material with
the applied field. The magnitude of the susceptibility is calculated from the imaginary part of the
ot

third-order NLO susceptibility (Im χ3) and real part of the third-order NLO susceptibility (Re χ3),
which are directly related to β and n2, respectively [33]. The calculated value of χ3 for DFC1, DFC2,
DFC3 and DFC4 are 6.64 ×10−6, 1.45 ×10−6, 8.77 ×10−6 and 3.52 ×10−6 respectively as shown in
tn

Table 5. The strong delocalization of π-electrons is the main cause for observing third-order NLO
properties in DFC1-DFC4. In this work, anthracene (DFC1), pyrene (DFC2), methyl furan (DFC3)
and trifluoromethyl (DFC4) are the electron-donating groups with different strength as substituents
with triphenylamine in the middle of the bridge connecting both substituted moieties through
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carbonyl groups which forms donor-π-donor (D-π-D) charge transfer group with extended π-
conjugation system. DFC3 with methyl furan (weak electron-donating group) attach to carbonyl
group (C=O) promotes the carbonyl group for pulling more electrons from the triphenylamine
moiety compared to the other compounds. As a result, charge transfer might occur easily in this
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extended π-conjugated molecular system, increasing the NLO activity. As compared to the
previously reported chalcone with D-π-A-π-A system [34], NLO susceptibilities (χ3) of DFC1-
DFC4 with D-π-D system are comparable under CW laser regime and these compounds also has
the potential for optoelectronic and NLO application.
Pr

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 Table 5. Third-order NLO parameters of DFC1-DFC4.

ed
DFC1 DFC2 DFC3 DFC4
β (x 10-4) cmW-1 5.75 1.26 7.59 3.05
-15
n2 (x 10 ) cm W 2 -1 -1.90 -1.27 -3.41 -2.28
Im χ(3) (x 10-6) e.s.u 6.64 1.45 8.77 3.52
(3) -14 -15
Re χ (x 10 ), *(x 10 ) e.s.u 1.38 *9.19 2.48 1.66

iew
χ(3) (x 10-6) e.s.u 6.64 1.45 8.77 3.52

v
re
er
DFC1 DFC2
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DFC3 DFC4
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Fig. 8. Open aperture curve of DFC1-DFC4

ep
Pr

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 ed
iew
DFC1 DFC2

v
re
er
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DFC3 DFC4
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Fig. 9. Closed aperture curve of DFC1-DFC4.

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3.8. 2nd Order nonlinear optical (NLO) properties: DFT calculation

Nonlinear optical (NLO) properties deal with the interaction of applied electromagnetic fields in
different materials to generate new electromagnetic fields, modified in wavenumber, phase, or other
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physical properties [35]. Density functional theory (DFT) calculations have been intrigued to be
useful in the description of the relationship between the electronic structure and their NLO response.
The parameters utilised to calculate and affect the NLO characteristic of the synthesised compounds
under investigation are tabulated in Table 6. The parameters include the relative electronic energies,
dipole moments, λmax, and HOMO and LUMO energy for DFC1-DFC4 computed at B3LYP / 6-
ep

311 G (d, p).

Pr

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 Table 6. The static dipole moment, first hyperpolarizability, and second hyperpolarizability of
DFC1 – DFC4 calculated at ω = 0, 0.

ed
Parameters DFC1 DFC2 DFC3 DFC4
µx -2.3763 -3.3191 -2.9753 -1.4272
µy 2.5629 1.6846 1.1233 5.8246

iew
µz 3.0106 2.8137 4.0900 1.2214
µtot 4.6129 4.6659 5.1810 6.1200

αxx -332.1722 -326.6697 -209.8959 -403.5677

αxy -36.7230 -42.6013 -35.5947 -21.0140
αyy -294.7142 -303.5236 -201.9178 -294.7774

v
αxz -8.0483 -3.3681 -7.7344 -0.4136
αyz -6.1428 -7.9805 -8.4900 -2.2658

re
αzz -291.9885 -334.3999 -226.6592 -306.9937
<α> 10-23 esu 4.5392 4.765 3.154 4.966
∆α 10-23 esu 1.135 1.189 1.013 1.623

βxxx -682.6629
er -546.0688 -567.7438 -343.4603
βyxx -177.2927 -252.4199 -345.1268 52.5034
βyyx 157.1892 -37.8606 152.4566 18.0846
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βyyy 159.5068 31.9739 25.9815 74.3007
βxxz 71.4140 385.4391 275.0758 90.3206
βyyz 50.5696 58.2437 47.5107 37.6996
βzxz 15.2918 47.3371 0.2204 21.4146
βzyz -19.9216 33.9175 5.8012 -43.2758
βzzz 13.9511 -2.9730 -6.4353 41.1934
ot

βtotal (10-30 esu) 5.3732 5.465 2.733 6.094

γxxxx -87929.0236 -100769.0862 -41760.9758 -113947.5471

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γyyyy -13682.0061 -19525.5184 -10816.7813 -17006.1821

γzzzz -5901.6524 -2199.0510 -1055.5797 -1990.5912
γxxyy -17171.2174 -20210.3527 -8606.4715 -21005.3593
γxxzz -14618.2877 -18468.8689 -8590.2534 -17559.9531
rin

γyyzz -3412.4944 -3952.9347 -2143.6143 -3319.3354

γtotal (10-35 esu) 1.792 0.375 0.929 2.183

Static dipole moment of all the synthesised compounds DFC1-DFC4 exhibit maximum 6 times
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greater values compared to the standard urea (1.3732 Debye), which is a known standard reference
compound for NLO characterisation. The higher dipole moment of the compound indicates the
efficient NLO response. From the synthesised compounds, DFC4 with higher dipole moments
reveals to have a stronger NLO response. This is because the presence of fluorine in the molecule
Pr

gives the huge difference in electronegativity which possessed a longer distance between the vector
charge in a molecule [36]. The value of dipole moment is directly proportional to the value of
polarizability. The higher value of dipole moment, the higher the value of polarizability. This is due
to the presence of higher redistribution of electron density that give the greater charge transfer. The

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 dynamic polarizability (α) with wavelength 532 nm for all compounds are 4.5392 x 10-23 esu
(DFC1), 4.765 x 10-23 esu (DFC2), 3.154 x 10-23 esu (DFC3), and 4.966 x 10-23 esu (DFC4). The

ed
polarizability values indicating that DFC4 with trifluoromethyl substitution (poor electron donating
group) led to a larger linear polarizability for the D-π-D chalcone derivatives. The 1st
hyperpolarizability (β) also at 532 nm for DFC1-DFC4 are 5.3732 x 10-30 (DFC1), 5.465 x 10-30
esu (DFC2), 6.094 x 10-30 esu (DFC3) and 2.733 x 10-30 esu (DFC4) respectively. It is noteworthy

iew
to note that all the synthesised compounds have larger β about 6 times compared to standard urea
(0.31 x 10-30 esu), which suggest that DFC1-DFC4 potential to be an efficient NLO materials. The
nature of electrical dipole moments in donor or acceptor substitution affects the enrichment in
hyperpolarizability values of the molecules, which gives an indicator on the NLO characteristic of
DFC1-DFC4. Due to the substantial effect from the CF3 groups that include the excellent charge
transfer mechanism from same least strength of group (CF3) throughout the conjugated molecular

v
backbone make DFC4 exhibit largest value of hyperpolarizability. Furthermore, the high value of
2nd-order hyperpolarizability (γ) is connected to the intermolecular charge transfer generated by the

re
delocalization of electron within D-π-D molecular framework. DFC4 exhibit the highest γ value.
The factors contributing to the highest γ value are the extensive π-electron conjugation and the
present of weak electron donor group of CF3. DFC4 reveals to have excellent nonlinear optical
response due to the fact that it possesses strongest linear polarizability, and the greatest values of
1st and 2nd order hyperpolarizability despite the highest energy band gap (3.01 eV) of the molecules,
er
due to the presence of least strength donor group substitution.
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4. Conclusion
In summary, both experimental and theoretical investigations are carried out to obtain the
information on the nonlinear optical (NLO) properties of four triphenylamine chalcone derivatives
with different donating substitution. The functional groups and molecular structures were elucidated
ot

and confirmed using 1H NMR and FTIR spectra. Thermal analysis results suggests That the
synthesised compounds are thermally stable in the range 228 – 333 °C. The UV-visible analysis
indicates the low cut-off wavelength possess in the range (288 – 433 nm) with narrow optical band
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gap (Egap) of (2.54 – 3.52 eV). DFT were calculated to obtain insight understanding of their
structure-property relationships. The NLO characteristic of DFC1 – DFC4 were performed using
the CW DPSS laser (532 nm, 200 mW). Results revealed the compounds to have positive nonlinear
absorption due to the occurrence of symmetric valley about the focus. The disubstituted chalcone
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derivatives of DFC1 – DFC4 with optical transparency in the visible region, low energy band gap,
excellent light harvesting energies and exhibit two-photon absorption suggest that DFC1 – DFC4
molecular structures have high potential candidate for the application as light emitting materials.
ep

Acknowledgements
The authors would like to acknowledge the financial support from Ministry of Higher Education
Malaysia for Fundamental Research Grants (FRGS/1/2020/STG05/UNIMAP/02/6), Institute for
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Medical Research, Malaysia for NMR analysis, Universiti Malaysia Perlis and Universiti Sains
Malaysia for research facilities and supports.

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 CRediT authorship contribution statement
Nurul Nabilah Shuaib: Writing – original draft, Visualization, Data curation, Methodology. Adibah

ed
Izzati Daud: Writing – review & editing, Validation, Supervision, Software, Resources, Project
administration, Funding acquisition. Suhana Arshad: Conceptualization, Resources, Methodology.
Mohamad Aizat Abu Bakar: Data curation, Methodology. Norazlan Mohmad Misnan:
Methodology, Data curation.

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