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OPEN Exploration of nonlinear optical

properties of 4‑methyl‑4H‑1,2,
4‑triazol‑3‑yl)thio)‑N‑phenyl
propanamide based derivatives:
experimental and DFT approach
Muhammad Irfan 1, Hammad Ali Khan 1, Shamsa Bibi 2, Gang Wu 3, Akbar Ali 1,
Samreen Gul Khan 1*, Norah Alhokbany 4, Faiz Rasool 5* & Ke Chen 3*

Triazoles, nitrogen-containing heterocycles, have gained attention for their applications in medicinal
chemistry, drug discovery, agrochemicals, and material sciences. In the current study, we synthesized
novel derivatives of N-substituted 2-((5-(3-bromophenyl)-4-methyl-4H-1,2,4-triazol-3-yl)thio)-N-
phenylpropanamide and conducted a comprehensive investigation using density functional theory
(DFT). These novel structural hybrids of 1,2,4-triazole were synthesized through the multi-step
chemical modifications of 3-bromobenzoic acid (1). Initially, compound 1 was converted into its
methyl-3-bromobenzoate (2) which was then transformed into 3-bromobenzohydrazide (3). The
final step involved the cyclization of compound 3, producing its 1,2,4-triazole derivative (4). This
intermediate was then coupled with different electrophiles, resulting in the formation of the final
derivatives (7a–7c). Additionally, the characterization of these triazole-based compounds (7a, 7b, and
7c) were carried out using techniques such as IR, HNMR, and UV–visible spectroscopy to understand
their structural and spectroscopic properties. The DFT study utilized M06/6-311G(d,p) functional to
investigate geometrical parameters, HOMO–LUMO energies, natural bond orbital analyses, transition
density matrix (TDM), density of states, and nonlinear optical (NLO) properties. The FMO analysis
revealed that compound 7c exhibited the lowest band gap value (4.618 eV). Notably, compound 7c
exhibited significant linear polarizability (4.195 >  × ­10–23) and first and second hyperpolarizabilities
(6.317 >  × ­10–30, 4.314 × ­10–35), signifying its potential for nonlinear optical applications. These NLO
characteristics imply that each of our compounds, especially 7c, plays a crucial part in fabricating
materials showing promising NLO properties for optoelectronic applications.

Compounds containing heterocyclic rings are important in the development of new classes of medicinal
­compounds1,2. The broad biological and pharmacological spectrum of heterocyclic molecules has sparked the
interest of researchers in recent years. Particularly, heterocyclic compounds containing azoles are ranked as of
special interest due to their strong synthetic and pharmaceutical ­applications3,4. Heterocyclic compounds have
been shown to exhibit great selectivity of action, minimal toxicity, and a therapeutic impact comparable to
that of traditional ­medications5. Heterocyclic compounds are specified to have carbon, oxygen, and other ele-
ments like nitrogen and sulfur within their cyclic ­rings6. Nitrogenous containing heterocycles such as triazoles
and their derivatives are interesting as they exhibit many structural characteristics of bioactive ­compounds7,8.
In 2023, Khram et al. reported the development of a novel method for the synthesis of 1,2,4-triazole- and
tetrazole-containing thiopyrano[2,3-b]quinolines and highlighted the potential of these compounds as anti-
viral ­drugs9. In the same year, Maghraby et al. conducted a comprehensive study to investigate a novel series

1
Department of Chemistry, Faculty of Physical Science, Government College University, Faisalabad 38000,
Pakistan. 2Department of Chemistry, University of Agriculture, Faisalabad, Pakistan. 3Department of Infectious
Diseases, The Affiliated Hospital of Southwest Medical University, Luzhou 646000, China. 4Department of
Chemistry, College of Science, King Saud University, 11451 Riyadh, Saudi Arabia. 5Institute of Chemical Sciences,
Bahauddin Zakariya University, Multan 60800, Pakistan. *email: [email protected]; faizrasoolbzu@
gmail.com; [email protected]

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of 1,2,3-triazole/1,2,4-triazole hybrids as antiproliferative agents targeting aromatase enzymes. Their findings

highlighted their potential as therapeutic agents. 10 In many research studies, 1,2,4-triazoles have been shown to
possess powerful biological properties, including ­antibacterial11,12, ­antimicrobial13,14, ­antifungal15, ­anticancer16,17,
antimycotic ­activity18, ­antinociceptive19, ­antioxidant20, ­anticonvulsant21,22, ­antiviral23, anti-inflammatory24, and
analgesic ­properties25.
Triazole building blocks are utilized in the synthesis of d ­ rugs 26, ­a grochemicals 27, ­d yes 28, and
­pharmaceuticals . They also find application as corrosion i­nhibitors31, stabilizers in ­polymers32, and ligands
29,30

in coordination ­chemistry33. Moreover, triazoles are utilized in the development of materials with unique prop-
erties, such as conducting polymers and s­ ensors34,35.
Additionally, these compounds hold promise for nonlinear optical (NLO) applications in various scientific
fields, including biophysics, chemical dynamics, surface interface presentations, medicine, materials, and nuclear
­sciences36,37. Computational calculations employing DFT are used to predict the electronic properties, including
non-covalent interactions, stability, magnetism, and nonlinear optical behavior, of organic c­ ompounds38,39. In
this context, DFT analysis has been employed to investigate the electronic properties, specifically the nonlinear
optical behavior, of 1,2,4-triazole derivatives.
Islam et al., in 2023, conducted a comprehensive study to investigate the influence of strain on the optical
properties of ­APbCl3 (A = K, Rb, Cs) perovskites using density-functional theory (DFT) models. The researchers
found that strain can improve the optical performance of these perovskites, resulting in enhanced absorption
and reduced optical l­ osses40. In a separate study conducted by Mushtaq et al. in 2023, the theoretical adsorption
of NOx gas molecules on the surface of CoFeMnSi quaternary Heusler alloys was investigated using density
functional theory calculations. The results of the study showed that NOx molecules act as charge acceptors by
attracting charge from the surface atoms of the Heusler alloys. This charge transfer process enhances the surface
reactivity and could potentially lead to improved gas sensing c­ apabilities41.
Rahman et al. (2023) conducted a comprehensive investigation on the optical and electronic properties of
­Sr3NCl3, with the aim of gaining valuable insights into its potential applications in the field of optoelectronics
and solar cell design. Their findings highlighted the potential of S­ r3NCl3 to exhibit strong visible light absorption
properties, with potential variations observed under increasing compressive (tensile) ­strain42. In another study,
Rahman et al. (2023) conducted a detailed analysis of the optical properties of ­Ca3AsI3 using first-principles
density-functional theory. Their research revealed that C ­ a3AsI3 exhibits exceptional optical properties, making
it highly suitable for efficient visible light ­absorption43. Furthermore, Rahman et al. (2023) utilized the first
principles DFT to explore how the optical and electronic characteristics of C ­ a3PI3 are impacted by strain. Their
findings demonstrated the strong absorption capabilities of C ­ a3PI3 in the visible r­ ange44. Overall, these studies
by Rahman et al. provide valuable insights into the optical and electronic properties of S­ r3NCl3, ­Ca3AsI3, and
­Ca3PI3, highlighting their potential in optoelectronics and solar cell design.
Joe et al. (2023) found that benzodiazepine compounds with N ­ O2 and Br substitutions exhibit 2-order
hyperpolarizability as well as self-focusing switching. Results indicate their applications in optoelectronics and
­photonics45. Khalid et al. (2023) formulated chromophores that exhibited significant nonlinear optical (NLO)
results. Their findings reveal that the compound PCMD8 demonstrated the smallest band gap of 2.048 eV,
efficient intramolecular charge transfer, and maximum energy of stabilization were i­ nvestigated46. Zainuri et al.
(2023) investigated compounds that demonstrate promising potential in nonlinear optical (NLO) applications,
such as optical limiting devices, due to their excellent structural stability and strong intermolecular ­interaction47.
This study aims to achieve two main objectives:1. Synthesis of novel 1,2,4-triazole core embedded den-
sity functionalized organic building blocks. 2. Exploration of optoelectronic behavior using density functional
­theory48,49. According to a literature review, NLO characteristics of triazole-based materials have not been
published yet. To fill this knowledge gap, the current work uses systematic structure–property interactions
to design and produce triazole-based isomers for energetic materials. The three triazole based derivatives;
2-((5-(3-bromophenyl)-4-methyl-4H-1,2,4-triazol-3-yl)thio)-N-(4-chloro-3-(trifluoromethyl)phenyl)propan-
amide, 2-((5-(3-bromophenyl)-4-methyl-4H-1,2,4-triazol-3-yl)thio)-N-(2-chlorophenyl)propanamide, and
2-((5-(3-bromophenyl)-4-methyl-4H-1,2,4-triazol-3-yl)thio)-N-(3-nitrophenyl)propenamide were synthesized.
The present study is of vital importance for evaluating the NLO uses of organic molecules. Hopefully, this study
will serve as the basis for developing entirely novel triazole-based organic dyes with exceptional NLO properties.

Materials and methods

General
Standard chemicals from Sigma Aldrich, Acros Chemicals, Macklin, and TCI were used without any addi-
tional purification. Silica gel 60 254F plates (Merck Germany) was used to perform TLC for reaction progress.
UV–visible spectra were measured and analyzed with high accuracy and precision by the Hitachi UV–Visible
Double Beam Spectrophotometer. A Stuart melting point apparatus was used to determine the melting point
of the samples.

Chemistry
A multi-step (three-step) procedure was adopted for the synthesis of triazoles starting form 3-bromobenzoic
acid as precursor. The synthetic route follows the synthesis of methyl-3-bromobenzoate (2) from 3-bromoben-
zoic acid (1) fallowed by converting it to 3-bromobenzohydrazide (3) and then converting that hydrazide into
5-(3-bromophenyl)-4-methyl-4H-1,2,4-triazole-3-thiol (4) as shown in Fig. 1. On the other hand, 2-chloro-
propanoyl chloride was reacted with different anilines (5a–5c) to obtain the desired N-substituted-2-Chloro-
N-phenylpropanamide (6a–6c). Finally, the derivatives (7a–7c) were prepared by the reaction between (4) and

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O
Br COOH Br COOCH3 Br NH2
NH
CH3OH / H2SO4 CH3OH / NH2NH2

1 Reflux at 80 oC for 3hr-4hr Reflux at 80 oC for 5hr-6hr

2 3

N N
Br SH
N
CH3 CH3OH / CH3N C S
o
4 Reflux at 170 C for 6hr-8hr

Figure 1.  Synthesis of 1,2,4-Triazole.

(6a-6c) under stirring with DMF as a solvent and LiH as a catalyst, as shown in Fig. 2. Complete structures of
(7a–7c) have been shown in Fig. S22.

General Synthesis Protocol for 2‑((5‑(3‑bromophenyl)‑4‑methyl‑4H‑1,2,4‑triazol‑3‑yl)

thio)‑N‑phenylpropanamide(7a–7c)
The triazole embedded derivatives were synthesized by 24 h of N-substituted 2-chloro-N-phenylpropanamide
(0.1 g) (5a–c), 5-(3-bromophenyl)-4-methyl-4H-1,2,4-triazole-3-thiol (0.1 g), LiH (0.05 g) and DMF (4 ml) in

N N O
SH Cl
Br
N HN
+
CH3 R

Stirring at 25oC for 30 min

4

10% Na2CO3/H2O
Stirring at 25oC for 5hr-6hr
DMF / LiH

NH2
O

R + Cl
Br O
H3 C Cl
R
N S 5(a-c)
N
H
N N CH3

(7a-c)

Cl
Cl H3 C O
H3 C O
N S
N S N
N CF3 H
H
N N CH3
N N CH3
Br
Br
7a O
7b
H3 C
N S
N NO2
H
N N CH3
Br
7c

Figure 2.  Synthesis of N-substituted triazole based derivatives.

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a round-bottom flask. TLC was used to check reaction progress. After reaction completion, the achieved pre-
cipitates were filtered off, washed with distilled water, and dried.

2‑((5‑(3‑bromophenyl)‑4‑methyl‑4H‑1,2,4‑triazol‑3‑yl)thio)‑N‑(4‑chloro‑3‑(trifluoromethyl)phenyl)propanamide
(7a)
Light blue amorphous. Percentage yield: 88%. MP: 182–184 °C. (λ max = 298 nm).IR (KBr, ­cm−1) 3220 (NH),
1695 (C=O), 1541 (N=N), 1483 (Ar–C=C), 1131 (C–N), 1032 (C–F), 728 (C–Cl). 1H-NMR (δ/ppm, 400 MHz,
­CDCl3): 10.87 (H-NH s, 1H), 8.15 (s, 1H, H-2′′), 7.79 (s, H-2′, 1H), 7.7 (H-6′,d, 1H, J = 12 Hz), 7.67 (1H, H-5′,t,
J = 12 Hz), 7.56 (H-4′,d, J = 8 Hz, 1H), 7.44 (H-5′′,d, 1H, J = 8 Hz), 7.4 (H-6′′,d, 1H, J = 8 Hz), 4.58 (H–S-CH, q,
1H, J = 8 Hz), 3.61 ­(CH3–N, s, 3H), 1.71 (­ CH3–CH, d, 3H, J = 4 Hz). 13C NMR (δ/ppm, 101 MHz, CDCl3): 169.57,
154.83, 152.57, 137.33, 133.82, 131.70, 131.49, 128.74, 128.43, 128.09, 127.72, 127.01, 126.49, 123.68, 123.18,
118.84, 44.86, 31.98, 16.77. GCMS: 519. Elemental Analysis: C, 43.91; H, 2.91; N, 10.78.

2‑((5‑(3‑bromophenyl)‑4‑methyl‑4H‑1,2,4‑triazol‑3‑yl)thio)‑N‑(2‑chlorophenyl) propanamide (7b)

White amorphous. Percentage yield: 82%. MP : 118–120 °C. (λ max = 297 nm). IR (KBr, c­ m−1) 3272 (NH), 1677
(C=O), 1591 (N=N), 1440 (Ar–C=C), 1163 (C–N), 747 (C–Cl). 1H-NMR (δ/ppm, 400 MHz, C ­ DCl3): 9.73 (s, 1H,
H-NH), 8.34 (H-6′,d, 1H, J = 8 Hz), 7.77 (H-2′, s, 1H), 7.66 (H-3′′,d, J = 8 Hz, 1H), 7.55 (H-4′,d, 1H, J = 8 Hz), 7.41
(H-5′,t, J = 8 Hz, 1H), 7.37 (H-5′′,t, J = 8 Hz, 1H,), 7.24 (H-6′′, d, 1H, J = 8 Hz), 7.05 (t, H-4′′, 1H, J = 8 Hz), 4.82
(H–S-CH, q, J = 8 Hz, 1H), 3.58 (­ CH3–N, s, 3H), 1.74 (­ CH3–CH, d, J = 8 Hz, 3H,). 13C NMR (δ/ppm, 101 MHz,
CDCl3): 169.46, 154.64, 152.26, 134.84, 133.63, 131.57, 130.55, 129.32, 127.93, 127.29, 127.21, 125.09, 124.38,
123.06, 122.54, 44.35, 31.87, 16.84. GCMS: 451. Elemental Analysis: C, 47.85; H, 3.57; N, 12.40.

2‑((5‑(3‑bromophenyl)‑4‑methyl‑4H‑1,2,4‑triazol‑3‑yl)thio)‑N‑(3‑nitrophenyl)propanamide (7c)
Yellow amorphous. Percentage yield: 93%. MP: 180–182 °C. (λ max = 296 nm). IR (KBr, c­ m−1) 3226 (NH), 1733
(C=O), 1694 (N=C), 1558 (N=N), 1522 (­ NO2), 1464 (Ar–C=C), 1164 (C–N). 1H-NMR (δ/ppm, 400 MHz,
­CDCl3): 11.0 (H-NH, s, 1H), 8.7 (H-2′′, s, 1H), 7.93 (H-6′,d, J = 8 Hz, 1H), 7.83 (H-4′′,d, J = 8 Hz, 1H), 7.79
(H-2′, s, 1H), 7.69 (H-6′′,d, 1H, J = 8 Hz,), 7.58 (H-4′,d, 1H, J = 8 Hz), 7.45 (H-5′′, t, 1H, J = 4 Hz), 7.42 (t, 1H,
J = 4 Hz, H-5′), 4.61 (H–S–CH, q, J = 8 Hz, 1H,), 3.63 ­(CH3–N, s, 3H), 1.73 ­(CH3–CH, d, 3H, J = 8 Hz). 13C NMR
(δ/ppm, 101 MHz, CDCl3): 169.61, 154.77, 152.74, 148.55, 139.51, 133.90, 131.53, 130.67, 129.49, 127.56, 127.12,
125.44, 123.19, 118.66, 114.58, 45.04, 32.13, 16.76. GCMS: 462. Elemental Analysis: C, 46.76; H, 3.49; N, 15.15.

Results and discussion

The spectroscopic examination identified synthesis of the compounds, as illustrated in Figs. S1–S21. Following
the determination of their structural conformation, a DFT investigation was conducted on the newly synthesized
molecules featuring 1,2,4-triazole functionalities. The specifics of this exploration are discussed below.

Frontier molecular orbitals (FMO)

To explore the optical as well as electronic properties of compounds, FMO analysis is a remarkable tool to evalu-
ate the probability of intramolecular charge transfer (ICT)50,51. HOMO demonstrates the ability to donate an
electron and is regarded as valence band, while LUMO reflects the capacity to accept an electron and is regarded
as conduction band. FMOs are the substantial source of transition energies that occur when an electron excites
from the HOMO to the LUMO. The energy difference (∆E = ELUMO–EHOMO) of compounds is directly associated
with their kinetic stability and chemical reactivity. A reduced energy difference (∆E) value results in increased
molecular polarizability, leading to an enhanced nonlinear optical (NLO) ­response52. ELUMO, EHOMO, and ∆E
values for A–C were calculated, and the outcomes are in Table 1.
The findings from Table 1 illustrates that by varying different groups in fragment 3, band gap of synthesized
compounds vary greatly. Compounds with large ∆E need more HOMO to LUMO energy of transition than those
with less energy difference hence making them preferable for NLO ­devices53–55. Therefore, compounds with lower
band gaps are compelling in the opto-electronic domain. In these synthesized compounds, fragments 1 and 2
are kept unaltered, while fragment 3 is modified, which results in different ΔE values. The HOMO energies of
synthesized molecules 7a, 7b, and 7c are determined as − 7.128, − 6.973, and − 7.144 eV, respectively, whereas
the LUMO energies are calculated as − 1.491, − 1.358, and − 2.526 eV, respectively. Consequently, the DFT-based
computed HOMO–LUMO energy gaps of synthesized molecules are 5.637, 5.615, and 4.618 eV, respectively.
Among the synthesized compounds, the maximum ∆E value (5.637 eV) is found in A, which has a chloro
group at the para position, and C ­ F3 group at the meta position. Due to negative inductive effect (−I) the chloro
group only slightly withdraws electrons, and it also releases electrons via resonance. Here, the resonance effect
dominates over the inductive effect and thus reduces the charge transference. Moreover, the ­CF3 group is an
electron withdrawing group due to the presence of three fluoro groups on the same carbon atom. Subsequently

Compounds EHOMO ELUMO ΔE

A − 7.128 − 1.491 5.637
B − 6.973 − 1.358 5.615
C − 7.144 − 2.526 4.618

Table 1.  The EHOMO, ELUMO, and  E of A-C, units in eV.

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B with two chloro groups in its structure showed reduced band gap. This chloro group at the ortho position has
a stronger electron-withdrawing effect, it would increase the charge transference in the molecule and potentially
reduce the band gap. Furthermore, the compound C, with a meta-positioned NO2 group, exhibits the lowest
band gap value, ascribed to the strong electron-withdrawing nature of the nitrogen atom, resulting in improved
charge transfer and a pronounced push–pull mechanism. Overall, the energy gap is observed in the following
decreasing order: A > B > C. Additionally, the outcomes for HOMO-1, LUMO + 1, HOMO-2, and LUMO + 2
energies, as listed in Table S1, provides further insights into the electronic structure and exciton dynamics of
these compounds.
Hence, among the three synthesized molecules (A, B, C) a smaller ∆E value is observed in C. The orbital
diagrams of HOMO and LUMO are presented in Fig. 3. For HOMO, the charge density of synthesized com-
pounds resides mainly on fragments 1 and 2, while LUMO charge density is hugely located on fragment 1 and
partly on fragment 2. These orbital diagrams are useful for analysing effective charge transfer in the synthesized
compounds. Therefore, high charge transition makes the synthesized compounds efficient materials for advanced
NLO devices.

Global reactivity parameters (GRPs)

Band gap is the most significant factor for the estimation of the global reactivity parameters (GRPs), such as
electron affinity (EA)56, ionization potential (IP)57, global hardness (η)58, global softness (σ)59, chemical potential
(μ)60, global electrophilicity index (ω)61, and electronegativity (X)62. It is an effective approach to predict global
trends in chemical reactivity using these characteristics. The EA and IP amplitudes of chemical compounds are
used for identifying their ability to capture and donate e­ lectrons63. The determination of electrophilic strength

HOMO LUMO

C
Figure 3.  The HOMOs and LUMOs of the compounds (A)–(C), illustrate the electronic cloud over the orbitals.

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in chromophores relies on these parameters, where higher values of chemical potential (μ) and hardness (η)
indicate increased kinetic stability. Additionally, these variables are directly linked to ∆E values and exhibit an
inverse relationship with global softness (σ). Therefore, molecules having smaller ∆E are more reactive, stable,
and soft with high polarization and serve as a finer competitor in providing the best NLO ­response64. Table 2
shows the outcomes for the computed GRPs of the examined chromophores.
By using Koopmans′ theorem (Eqs. 1–7), the chemical hardness (η), chemical potential (μ), electronegativity
(X), global softness (σ), and electrophilicity index (ω) are ­calculated65,66.
IP = −EHOMO (1)

EA = −ELUMO (2)
Electronegativity (X) and chemical potential (μ) are calculated using Koopmans’s theory as:
[ELUMO + EHOMO ]
X=− (3)
2

EHOMO +E LUMO
µ= (4)
2
The global softness (σ) and chemical hardness (η) can be calculated through Eqs. (5) and (6).
η = IP − EA (5)

1
σ = (6)
η
The electrophilicity index (ω) is reported by Parr et al.43,67. as:
µ2
ω= (7)
2η
From Table 2, compound C exhibits the highest ionization potential (IP) value among the synthesized
chromophores (7.144 eV), suggesting efficient charge distribution among its fragments. In contrast, compound
B exhibits the lowest ionization potential (IP) value of 6.973 eV, while compound C has the highest value of
7.144 eV. The ionization potential values follow the order B < A < C. Additionally, compound C demonstrates the
highest electron affinity (EA) value of 2.526 eV, while compound B has the lowest value of 1.358 eV. It is notewor-
thy that the ionization potential values are generally higher than the electron affinity values for compounds A, B,
and C. According to the literature, higher IP values indicate more chemical inertness and s­ tability68. Chemical
potential (μ) describes the molecular s­ tability69 by relating to molecular electronegativity. The negative μ value
indicate that the compound accepts electrons ­readily70. Similarly, the negative chemical potential values shown
by the synthesized compounds indicate their stable nature.
The order of global hardness (η) follows the trend C < B < A, correlating with the increasing energy gap (Egap).
This indicates that harder molecules with higher ∆E values exhibit greater stability and lower reactivity. Global
softness (σ) is also linked to chemical potential and plays a role in understanding reactivity and stability. The
increasing order of σ is given as A < B < C. This ascending order is opposite to the increasing energy gap order,
representing A (0.177 eV) with the least reactivity; however, C (0.216 ­eV−1) is highly reactive showing highest
softness value among the synthesized compounds. Overall, Egap order and global reactivity descriptors have a
very good association. Low-lying Egap is admitted to showing high molecular nonlinear behavior. The remarkable
nonlinear optical (NLO) responses observed in the tested systems strongly indicate their potential for significant
applications in optoelectronics.

Density of states (DOS) analysis

The DOS further supports the findings of the FMO analysis by confirming electronic delocalization in the HOMO
and LUMO o ­ rbitals71. Determining the distribution of electron charge on molecular orbitals by computing the
DOS percentages for HOMOs and LUMOs offers additional support for the idea that the electron charge patterns
are influenced by the differences in fragment 3. To comprehend the DOS, we segmented our chromophores into
three components, namely, fragments 1, 2, and 3. The illustration in Fig. 4 depicts these fragments using red,
green, and blue lines, correspondingly. Along the x-axis of DOS graphs, negative values denote the valence band

Compounds IP EA X Μ Η ω σ ΔNmax
A 7.128 1.491 4.309 − 4.309 2.818 3.294 0.177 1.529
B 6.973 1.358 4.165 − 4.165 2.807 3.090 0.178 1.483
C 7.144 2.526 4.835 − 4.835 2.309 5.062 0.216 2.093

Table 2 .  Computed global reactivity parameters of A-C, units in eV.

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(HOMO) whereas, positive values indicate the conduction band (LUMO). The energy gap is represented by the
space between HOMO and ­LUMO72.
Figure 4 illustrates that the HOMO electron density of compound A is primarily located on fragment 3, while
the LUMO charge density is predominantly distributed on fragment 3 and partially on fragment 2. In case of B,
the HOMO charge density is mostly found on fragment 2, and fragment 3 having a small contribution, while the
LUMOs are dispersed across fragment 2. For compound C, HOMOs are evenly distributed throughout fragments
2 and 3, but the LUMOs of the same compounds are located only on fragment 2. Table S9 demonstrates that for
compounds A–C, fragment 1 contributes 46.8, 36.1, and 49.7% to HOMO and 53.5, 59.9, and 0.0% to LUMO,
respectively, while fragment 2 contributes 51.5, 60.8, and 49.6% to HOMO and 40.8, 39.4, and 0.4% to LUMO,
accordingly. Similarly, fragment 3 contributes 1.7, 3.1, and 0.7% to HOMO and 5.7, 0.7, and 99.6% to LUMO,
respectively. The maximum HOMO charge density for compound A appears on fragment 2 at − 6.5 eV, while
the highest LUMO charge density is found on fragment 3 at 1.5 eV, confirming an effective charge transfer from
fragment 2 to fragment 3. In case of B, fragment 2 is found to have the greatest HOMO density at 7.2 eV whereas
fragment 1 has the highest LUMO density. For C, fragment 1 depicts the highest maximum HOMO density of
about 7.1 eV, whereas fragment 3 exhibit the highest maximum LUMO density of around 0.5 eV. This type of
charge density favours the charge transfer from HOMO of fragment 1 to LUMO of fragment 3 via fragment 2.
These findings demonstrate the importance of manipulating various components in fragment 3 to create diverse
chromophores, influencing the transmission of electronic charges through distinct pathways. Overall, the results
of DOS analysis significantly correlate with the outcomes of the FMO study.

Transition density matrix (TDM) analysis

The TDM is widely used to illustrate hole-electron pair dynamics and to explore nature of transitions in the
examined ­compounds73. TDM analysis assists in the evaluation of electronic charge excitation processes, transi-
tions from the ground state ­(S0) to excited state ­(S1), and electron–hole pair localization and delocalization. The
TDM heat maps provide information about the nature of transition in these synthesized ­chromophores47. Fig-
ure 5 displays the transition density matrix (TDM) maps for all synthesized compounds, depicting the charge
density transfer between the three distinct components (fragments 1, 2, and 3) of each chromophore. It is worth
noting that the influence of hydrogen atoms on electronic transitions is not discussed in this study due to their
minimal contribution.
Figure 5 depicts that in compounds A and B, the higher electronic cloud is clearly visible by green and red
dots on fragment 3 and 2 of the heat maps. This electronic cloud exploited the successful transfer of electrons.

Figure 4.  The DOS plots of the titled compounds (as segmented into three fragments: 1, 2, and 3 are shown
with red, green, and blue lines, respectively).

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However, compound C heat map shows that the electronic cloud is primarily on fragment 2, with a small amount
of charge also visible on fragment 3. Such a pattern of electronic cloud facilitates the electron density to migrate
towards fragment 3 without trapping. The presence of the very electron-deficient group (-NO2) on fragment 3 of
compound C may be the reason for this peculiar b ­ ehavior74. The TDM heat maps show efficient charge transfer
coherence without any trapping in any of the investigated chromophores. These visual representations of TDM
indicate a more straightforward and enhanced exciton dissociation in the excited state, facilitating the advance-
ment of materials for NLO applications.

Natural population analysis (NPA)

The computation of effective atomic charges, which shows the distribution of positive and negative charges
among atoms in the molecule, is essential for determining whether the length of the bonds between the atoms
should increase or decrease. Atomic charges have an impact on the dipole moment, electrostatic potential sur-
face, electronic structure, molecular polarizability, and numerous other properties of molecular s­ ystems75,76.
Figure 6 demonstrates the results of an NPA analysis to determine the natural charges of A–C compounds. The
process of charge transformation that results from reactions, as well as electrostatic potential on system surfaces
are all commonly assessed using the natural charge e­ xamination77. The arrangement of molecules and their
bonding capabilities are heavily impacted by the electrical charges carried by individual atoms. Natural charges
of the molecules under investigation reveals that the presence of electronegative elements such as O, F, Cl, and
Br are responsible for an uneven redistribution of the electron density across the benzene r­ ings78. Additionally,
Mulliken population analysis confirm that all of the hydrogen atoms have the same charge distribution, with the
negative charges on carbon atoms leading to positive charges on hydrogen atoms.
From NPA, it can be observed that positive charges are present on all H, S, and Br-atoms. However, some
C atoms have a positive charge while others have a negative charge. The presence of large negative charge on C
atoms is due to their involvement in resonance with neighbouring N and O atoms. All N, Cl, and F-atoms were
negatively charged except one nitrogen in compound C. Here it can be seen that C34 of compound A, C28 of

Figure 5.  The TDM maps of compounds (A)–(C) (as segmented into three fragments: 1, 2, and 3 are shown
diagonally charge transference between these segments).

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Figure 6.  Natural population analysis graph of all the synthesized compounds illustrated the presence
of electronegative elements.

compounds B and C showed a higher positive charge while N32 of compound A, N31 of compound B and C
has a higher negative charge (see Fig. 6).

Natural bond orbital (NBO) analysis

NBO analysis confirm the presence of hydrogen bonds resulting from hyper-conjugated interactions in the
investigated ­chromophores79. Because all the orbitals are mathematically selected to include the highest possible
percentage of the electron density, it provides the most precise representation of the natural Lewis structure.
The NBO analysis effectively explains the interaction between the filled and virtual orbital space ­information80.
­ (2) related to the delocalization i → j for each donor (i) and acceptor (j)
In Eq. (8), the stabilization energy E
is calculated by second-order perturbation t­ heory81.
 2
Fi,j
E (2) = �Eij = qi   (8)
Ej − Ei

where F(i. j) is the off-diagonal NBO Fock matrix member, i and j are diagonal elements, and qi is the donor
orbital occupancy, while, Ei and Ej illustrate off-diagonal NBO Fock or Kohn–Sham medium elements 82,83. The
stabilization energies of several orbitals have been examined and are presented in Tables S2–S4, while important
transitions are depicted in Table 3.
To enhance the interaction between the electron-donating and electron-accepting components, increased
stabilization energies E(2) are necessary. With increasing E(2) value, the interaction between electron-deficient and
electron-rich molecules becomes stronger. The studied compounds have six distinct transitions, namely π → π*,
σ → σ*, π → σ*, σ → π*, LP → π*, and LP → σ*. However, the most prominent transitions are π → π*, σ → σ*,
LP → π*, and LP → σ*. But the most dominant transitions are π → π*, followed by LP → π* and LP → σ*, while
σ → σ* is the least dominant among all 84.
From Table 3, it is evident that in A, the greatest value of the most probable transition
π(C12–C17) → π*(C15–C16) has been found to be 27.04 kcal/mol, the most dependable transition that results
in the highest stabilization energy and a robust connection between donor (π) and acceptor (π*) units. π(C5–C6)
to π*(C21–N44) transition, which had E(2) value of 15.42 kcal/mol, was considered to be the least stable. Similarly,

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Compounds Donor (i) Type Acceptor (j) Type E(2) [kcal/mol] E(j)-E(i) [a.u.] F(i,j) [a.u.]
C12-C17 π C15-C16 π* 27.04 0.29 0.08
C5-C6 π C21-N44 π* 15.42 0.29 0.059
N44-N45 σ C23-S24 σ* 7.02 1.02 0.076
A
N22-C23 σ C40-H43 σ* 0.51 1.2 0.022
N22 LP (1) C21-N44 π* 48.4 0.31 0.111
F36 LP (1) C15C34 σ* 0.5 1.47 0.025
C13-C14 π C12-C17 π* 24.87 0.3 0.077
C28-O30 π C22-N38 π* 0.6 0.41 0.016
C2-C7 σ C3-Br33 σ* 5.43 0.83 0.06
B
C17-N31 σ N31-H32 σ* 0.54 1.2 0.023
N31 LP (1) C28-O30 π* 55.33 0.33 0.121
S23 LP (2) C39-H42 σ* 0.5 0.62 0.016
C12-C13 π C14-C15 π* 27.71 0.28 0.079
C28-O30 π C22-N40 π* 0.63 0.41 0.016
N39-N40 σ C22-S23 σ* 7.02 1.02 0.076
C
C13-H19 σ C12-H18 σ* 0.57 0.96 0.021
O37 LP (3) N35-O36 π* 179.33 0.16 0.154
S23 LP (2) C12-C13 π* 0.54 0.28 0.012

Table 3.  Chosen NBO analysis results for the examined chromophores (A-C).

transitions like σ(N44–N45) → σ*(C23–S24) and σ(N22–C23) → σ*(C40–H43), have maximum and minimum
E(2) values of 7.02 and 0.51 kcal/mol, correspondingly. The outputs of these stabilization energies result from a
weak interaction between π and π*. Electronic interactions such as LP1(N22) → π*(C21–N44) with the greatest
stabilization energy value of 48.4 kcal/mol and LP1(F36) → σ*(C15–C34) with the lowest value of 0.5 kcal/mol
were identified when the phenomena of resonance were taken into consideration.
The transition π(C13–C14) → π*(C12–C17) is the dominant π → π* transition depicted by B with E(2) of
24.87 kcal/mol on the other hand, π(C28–O30) → π*(C22–N38) possess least E(2) value at 0.6 kcal/mol. Due
to enervated connections between the donor and acceptor, the transitions σ(C2–C7) → σ*(C3–Br33) and
σ(C17–N31) → σ*(N31–H32) have the maximum and minimum energy values of 5.43 and 0.54 kcal/mol, cor-
respondingly. In addition, resonance resulted in the stabilization energies of additional electronic transitions,
such LP1(N31) → π*(C28–O30) and LP2(S23) → σ*(C39–H42) being 55.33 and 0.5 kcal/mol, respectively.
Data from Table 3 reveals that the compound C demonstrated that the transition π(C12–C13) → π*(C14–C15)
had the least stabilization energy (0.63 kcal/mol) while the transition π(C28–O30) → π* (C22–N40) had the high-
est stabilization energy (27.71 kcal/mol). Weak interactions cause the transitions σ(N39–N40) → σ*(C22–S23)
and σ(C13–H19) → σ*(C12–H18) to have senergies of 7.02 and 0.57 kcal/mol, correspondingly. The maximum
energy discovered for LP → π* transition is 179.33 kcal/mol for LP3 (O37) → π*(N35–O36), while the lowest
energy of LP → σ* is found to be 0.54 kcal/mol for LP2 (S23) → σ* (C12–C13).

Nonlinear optical (NLO) properties

The development of materials with improved NLO behavior is required for the development of electro-optic
modulation, frequency mixing, enhanced data rates, and harmonic generation related to the technology of
potential ­communication85,86. Champagne and Bishop developed an intriguing topic by examining the effects
of NLO on organic ­molecules87. Organic polymeric as well as heterocyclic compounds with significant hyper-
polarizability amplitudes have attracted attention due to their potential use in NLO materials. Many research
efforts develop effective methods for synthesizing organic chromophores in the NLO field because of their dis-
tinctive ­properties88. Compounds A-C have all been examined in the present study for possible NLO features
by computational and experimental calculation. Based on the electronic characteristics, it is estimated that the
intensity of the optical reactions would record a progressive linear as well as nonlinear r­ esponses89. The dipole
moment (µtot), polarizability < α > , first-order hyper-polarizability (βtot), and second-order hyper-polarizability
(γtot) values of the synthesized compounds computed by Eqs. (9)–(12) are shown in Table 4. Tables S5–S8 dem-
onstrate the detailed outcomes for all tensors.
 1/2
µ = µ2x + µ2y + µ2z (9)

�α� = 1/3(αxx + αyy + αzz ) (10)

2
βtot = (β(x) + βy2 + βz2 )1/2 (11)

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Compounds µtot < α >  × ­10–23 βtot × ­10–30 < γ >  × ­10–35

A 5.606 4.324 5.565 3.956
B 4.222 4.109 5.240 3.605
C 5.866 4.195 6.317 4.314

Table 4 .  Computed dipole polarizability (µtot) in Debye, average polarizability < α > , first hyperpolarizability
(βtot) and second hyperpolarizability < γ > in esu of the A-C compounds.


γtot = γx2 + γy2 + γz2 (12)

1 
Where γi = (γijji + γijij + γiijj ) i, j =
15 j

An essential consideration for determining the polarizability of organic chromophores is the dipole moment
(µtot)90 which is the measure of the separation of charges. The µtot of chromophores A–C is found to be 5.606,
4.222, and 5.866 D, respectively. Compound C has the highest total value of all the compounds (5.866 D), which
may be due to the presence of a potent electron-withdrawing group N ­ O2. On the other side, B which has a weak
electron withdrawing chloro group in fragment 3, has the lowest value of dipole moment at 4.222 D. The overall
increasing order of dipole moment is B < A < C. The prominent values of µy (4.697, 3.718, and 5.066 D, respec-
tively), shown in Table S5, suggest that the greater polarity for compounds A–C resides along the y-axis (ordi-
nate). Furthermore, on comparing the outcomes with standard para-nitroaniline chromophore (µpara-nitroaniline = 6.3
D), it is observed that the newly synthesized compounds exhibit better polarity than standard p-NA.
The average polarizability was observed to be the highest in compound A (4.324 × ­10–23 esu). The lowest value
of < α > , on the other hand, was found in B (4.109 × ­10–23 esu). This was because of the presence of the ­CF3 group
along with the chloro group that enriched the electron density and improved the electron-withdrawing capacity.
The < α > values of A–C are 4.324 × ­10–23, 4.109 × ­10–23, and 4.195 × ­10–23 esu, accordingly and tensors of < α > are
duslpayed in Table S6. According to the literature, molecule polarizability is influenced by the HOMO–LUMO
energy ­gap91. The HOMO–LUMO energy gap is inversely related to both linear and nonlinear polarizabilities.
Small HOMO–LUMO energy gap compounds enable high nonlinear and linear polarizabilities. In contrast to
the energy gap values for A, B, and C, a small energy gap for C is seen in our analysis. As a result, its linear and
nonlinear polarizability values are higher.
Among all of the developed compounds, the highest value of βtot was observed in C at 6.317 × ­10–30 esu as it has
a powerful electron-withdrawing unit − ­NO2. A slight decrease in βtot value was found in A i.e., 5.565 × ­10–30 esu.
However, the lowest value of βtot was observed in B (5.240 × ­10–30 esu). First-order hyper-polarizability responses
of A–C were 401.5616, 1605.112, and 1298.838 times greater than that of the p-NA (3.610 × ­10–34), respectively.
For each of the investigated chromophores, a notable secondary hyperpolarizability was observed in the y-axis
direction, as illustrated in Table S7, with C having a greater value of γtot among the derivatives. The decreasing
order of second-order hype-polarizability (γtot) values is shown as: C > A > B. In a comparative investigation, we
also studied the non-linear optical characteristics of p-NA (3.812 × ­10–36) used as the standard chromophore.
This comparison with p-NA demonstrates that compounds A–C, with compound C being the most effective
among them, are efficient candidates for NLO materials. The reasoning above also leads to the conclusion that
introducing different groups in fragment 3 results in yielding significant NLO amplitude.

Conclusion
In the current research, synthesis of three novel N-substituted 2-((5-(3-bromophenyl)-4-methyl-4H-1,2,4-triazol-
3-yl)thio)-N-phenylpropanamide derivatives have been reported in multiple step approach. The structures of
these compounds were analyzed by spectroscopic analysis. These spectral analyses provided crucial evidence
supporting the structural integrity of the synthesized compound. All synthesized hybrids (7a–7c) exhibited
UV–Vis absorption spectrum within the range of 298 nm, 297 nm, and 295 nm. IR spectra confirmed the pres-
ence of specific functional groups peaks associated with NH groups 3272–3158 c­ m−1, carbonyl groups (C=O)
1733–1677 ­cm−1, N=C 1694–1641 c­ m−1, and N=N 1596–1526 c­ m−1, and aromatic C=C stretching 1480–1440
­cm−1 while NMR spectra detected quartets, singlets, and doublets, at 4.58–4.82, 3.55–3.65, and 1.71–1.75 ppm,
and H-4′ and H-5′ contained triplets at 7.39–7.67 ppm in all compounds’ spectra (7a–7c). According to the
FMO data, compound C had the lowest band gap of 4.618 eV. Additionally, global reactivity parameters were
also correlated to the band gap, compound C exhibits the lowest global hardness of 2.309 eV and the highest soft-
ness value of 0.216 eV. Furthermore, higher values of NBO-based hyper conjugative interactions were noted,
endorsing the highest stability of the molecules under investigation. The charge distribution and electrophilic
and nucleophilic areas of the examined chromophores were explained by natural population analysis Accord-
ing to TDM heat maps, the reduced band gap will help the effective transmission of charges from fragment 2 to
fragment 3. DOS pictographs provide more support to this efficient transfer of electronic cloud. Moreover, the
synthesised compound C exhibits a notable large NLO response with values of 5.866 D, 4.195, 6.317, and 4.314
esu for µtot, < α > , (βtot) and < γ > , respectively. Based on the FMO data, compound C exhibits the lowest band
gap, highest stability, lowest global hardness, and highest softness values. Furthermore, its reduced band gap

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and notable large NLO response suggest its suitability for applications that require efficient charge transmission
and strong NLO properties. These findings contribute to the understanding of the structure–property relation-
ships and pave the way for further exploration and utilization of these compounds in optoelectronic and related
applications.

Computational procedure
At first the structure of yielded compounds were optimized at M06/6-311G(d,p) functional with the aid og Gus-
sian 09 software. After getting the true minima geometries of A–C chromophores, different kind of analyse like
FMOs, NPA, NLO, DOS and TDM were accomplished at DFT/TDDFT approached by utilizing above-mentional
level. Different software like PyMOlyze 2.0 program O ­ rigin92 and Gauss ­Sum93 were utilized to interprete the
data from jobs.

Data availability
All data generated or analyzed during this study are included in this published article and its supplementary
information files.

Received: 1 October 2023; Accepted: 9 January 2024

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Acknowledgements
K.C. acknowledges the support from the doctoral research fund of the Affiliated Hospital of Southwest Medi-
cal University. The authors extend their sincere appreciation to Researchers Supporting Project number
(RSP2024R253), King Saud University, Riyadh, Saudi Arabia.

Author contributions
M.I.: Conceptualization; methodology. H.A.K.: Methodology; software; project administration. S.B.: Concep-
tualization; resources. G.W.: Conceptualization; methodology; software. A.A.: Data curation; formal analysis;
validation. S.G.K.: Data curation; formal analysis. N.A.: Data curation; formal analysis. F.R.: Conceptualization;
methodology; software. K.C.: Conceptualization; resources.

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Competing interests
The authors declare no competing interests.

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