Optik 164 (2018) 5–15

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Optik
journal homepage: www.elsevier.de/ijleo

Original research article

Design, characterization and nonlinear optical properties of

coumarin appended chalcones: Use of a dual approach
Shabbir Muhammad a,b,∗ , Abdullah G. Al-Sehemi b,c , Mehboobali Pannipara b,c ,
Ahmad Irfan b,c
a
Department of Physics, College of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia
b
Research Center for Advanced Materials Science (RCAMS), King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia
c
Department of Chemistry, College of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia

a r t i c l e i n f o a b s t r a c t

Article history: In present investigation, we present designing and characterization of coumarin

Received 27 January 2018 appended chalcone hybrids using a dual approach consisting of experimental and
Accepted 27 February 2018 computational techniques. For the first time, the parent compound 2 ((E)-2-(3-(2,4-
dimethoxyphenyl)acryloyl)-3H-benzo[f]chromen-3-one) is successfully synthesized in our
Keywords: lab. The compound 2 is characterized experimentally as well as quantum computational
Nonlinear optical techniques. The results of absorption and emission spectra are compared with those of com-
Chalcones
putationally calculated spectra. A good agreement is found among the experimental and
Coumarin
calculated spectra of compound 2. The experimental absorption spectra show maximum
First hyperpolarizability
Second hyperpolarizability absorption and emission peaks at 392 and 461 nm, which are found to be in agreement
with their experimental absorption and emission peaks at 393 and 501 nm, respectively.
Additionally, we perform analysis of its nonlinear optical (NLO) properties by calculating its
second-(ˇ) and third-order <␥> nonlinear polarizabilities. The compound 2 shows reason-
ably good NLO response with its ˇ and <␥> amplitudes mounting to 120.23 × 10−30 esu and
677.12 × 10−36 esu, respectively. These ˇ and <␥> amplitudes of compound 2 are ∼6 and
∼20 times larger than those of para-nitroaniline (PNA) at BMK/6-311G** level of theory.
Based on above structure-property relationship, we also check the effect of substitution
of donor groups in the form of further four derivatives i.e. 2a, 2b, 2c and 2d. Interest-
ingly, among these derivatives, the derivative 2d shows a robust NLO response with its ˇ
and <␥> amplitudes as large as 218.84 × 10−30 esu and 1515 × 10−36 esu, respectively. The
present investigation not only reports the first synthesis of compound 2 but also explores
the potential of compound 2 and its derivatives as efficient NLO-phores.
© 2018 Elsevier GmbH. All rights reserved.

1. Introduction

Among the advanced functional materials of modern scientific era, optical and NLO materials are the most intriguing
materials. Optical materials are used as semiconducting materials and light emitting diodes while NLO materials functions
in telecommunication, optical data storage and laser frequency conversion etc. [1–3]. With the advancement of modern
technology, there is always a dire need to produce new NLO materials with more efficient NLO properties. Over the past

∗ Corresponding author at: Department of Physics, College of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia.
E-mail address: [email protected] (S. Muhammad).

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6 S. Muhammad et al. / Optik 164 (2018) 5–15

several years, NLO properties have studied in several types of materials [4] mainly including organic [3], inorganic [5],
organometallic [6] and other types hybrid materials [7]. It is important to pinpoint that every class of materials has different
pros and cones owing to their practical applications. Nevertheless, organic class is considered to be the most studied class of
material for NLO properties [8]. Due to the vast variety of functional groups and a great diversity among designing strategies,
organic class has been always the best choice for tuning NLO properties. Additionally, organic NLO materials also enjoy the
advantage of being cost effectiveness and ease of their fabrication for the device applications [4].
Among several organic compounds, the chalcone derivatives are extensively studied materials for their biological activ-
ity and electrochemical properties. Recently, several studies focused on the chalcones for their interesting NLO properties
[9–11]. Furthermore, chalcone derivatives also possess excellent electrochemical and optical properties like high extinction
coefficients and broad absorption range in UV spectrum etc. [12]. On the other hand, the coumarin compounds are important
member of organic class of materials, which occur and synthesized naturally among many plants. The coumarin compounds
have a range of pharmaceutical applications ranging from anti-cancer to antioxidant activities [13]. In view of above inter-
esting properties of chalcone and coumarin compounds, some recent attempts have been made to synthesize the hybrid
coumarin-appended chalcone derivatives [14–16]. These coumarin-appended chalcone derivatives have been studied for
their potential spectroscopic and optical properties. In most of the coumarin-appended chalcone derivatives, the coumarin
moiety acts as electron acceptor group establishing the donor acceptor type configurations [17]. Huang et al. reported the
synthesis and characterization of indole and anthracene based coumarines having two photon induced fluorescent properties
[14]. The synthesis and characterization of chalcone and coumarin-based chromophores are also important to mention here,
where benzocoumarin systems showed significant bathochromic effect i.e. ∼100–500 cm−1 as compared to the coumarin
systems [16]. Similarly, Sun et al. have also reported the synthesis of coumarin-based chromophores having azo and pyrazo-
line moieties [15]. Along above lines, Xue et al. report another important study, which theoretically explains the structure and
optical properties of coumarin-based chromophores [17]. In our recent studies, we have explored several novel strategies to
tune the NLO properties of chalcone compounds, which include the effect of number and position of methoxy groups [18],
tuning of push-pull configuration [19] as well as the effect of bridging groups [20] etc. To the best of our knowledge, there
is no experimental and/or computational study that targets the nonlinear optical properties (second- and/or third-order
polarizability) of coumarin-appended chalcone derivatives. The coumarin compounds possesses important photophysical
properties due to their structural resemblance with other heterocyclic dyes [21]. Several compounds with heterocyclic moi-
eties showed interesting NLO properties. So, it will be interesting to explore the potential of coumarin-appended chalcone
derivatives possessing push-pull configurations for NLO applications. The present study will not only highlight the synthe-
sis of important coumarin-appended chalcone derivative but also extends the number of derivatives through the use of
quantum chemical methods to get a structure-NLO property relationship among these derivatives as it will be discussed in
succeeding sections.

2. Methodology

2.1. Experimental details

Analytical grade chemicals and solvents used in this study were used without further purification. Reaction was monitored
by thin layer chromatography (TLC) with the aid of UV light. 2-Hydroxy-1-naphthaldehyde, 2, 4-Dimethoxybenzaldehyde
and ethylacetoacetate were purchased from Sigma–Aldrich and Merck. Stock solution of the title compound and its dilu-
tions were prepared for UV–vis and fluorescent study at different concentrations. Gallenkamp melting point apparatus was
used to determine the melting point and the infrared (IR) spectra were recorded on Shimadzu FT-IR 8400S infrared spec-
trophotometer using KBr pellets. The NMR (1 H and 13 C) spectra were recorded on a Bruker DPX-600 at 600 MHz and 150 MHz,
respectively, using TMS as the internal standard. The chemical shift values are documented on ␦ scale and coupling constants
(J) in Hertz; Splitting patterns were entitled as follows: s: singlet; d: doublet; m: multiplet. PG UV-160A spectrophotometer
was used to record the UV–vis electronic absorption spectra, and the steady-state fluorescence spectra were measured using
Varain Cary Eclipse spectrofluorophotometer using a rectangular quartz cell of dimensions 0.2 cm × 1 cm.
Procedure for the Synthesis of 3-acetyl-3H-benzo[f]chromen-3-one (1)
To a solution of 2-Hydroxy-1-naphthaldehyde (860 mg, 5 m mol) and ethylacetoacetate (650 mg, 5 m mol) in ethanol
(40 ml), 0.3 mL of piperidine and 2–3 drops of glacial acetic acid were added. The mixture was refluxed for 5 h. After the
completion of the reaction as identified by TLC, the reaction mixture was cooled to room temperature and 20 mL of ice cold
water was added. The solid product was collected by filtration, dried and recrystallized from ethanol to give 2 (480 mg).
Yield 69%, off white solid, Melting point: 168 ◦ C; IR (KBr, v cm−1 ): 1660 (CO), 1735 (CO), 1497, 1420, 1232, 792, 657; 1 H NMR
(600 MHz, CDCl3 ): ı 8.2 (d,1H, Ar-H), 7.84(d,1H, Ar-H), 7.64 (m, 4H, Ar-H), 8.72 (s,1H, Ar-H), 2.27 (s, 1H, −CH3 ); 13 C NMR
assignments 13 C NMR (150 MHz, CDCl3 ) ı 192.20 ( CO CH3), 140.2 (C C), 138.9 (C C), 142.2 (C C), 145.6 (C C), 150.96
(C C), 131.27 (C C), 165.07(O CO ring), 125.22 (C C), 123.90 (C C), 127.40(C C), 149.45 (C C), 22.18 ( CH3), 124.03
(C C), 124.72 (C C).
Procedure for the Synthesis of 2-[3-(2,4-Dimethoxy-phenyl)-acryloyl]-benzochromene-3-one (2)
To a solution of 3–Acetyl coumarin (480 mg, 2 m mol) and 2, 4-Dimethoxybenzaldehyde (335 mg, 2 m mol) in ethanol
(50 ml), 0.3 mL of piperidine and 2–3 drops of glacial acetic acid were added. The mixture was refluxed for 12 h. After the
completion of the reaction as identified by TLC the solvent was removed under vacuum. The residue thus obtained was
 S. Muhammad et al. / Optik 164 (2018) 5–15 7

Fig. 1. The graphical representation of second-(␤) and third-order polarizability (␥) of compound 2 with different DFT methods.

triturated with 10 mL of ethanol until the formation of fine precipitates. The precipitate was filtered off and recrystallized
from methanol to give 2 (522 mg, 68%) as pale yellow solid.
Yield 76%, Pale yellow solid; Melting point: 204–206 ◦ C; IR (KBr, v cm−1): 1690 (CO), 1745 (CO), 1497, 1420, 1232, 802,
648; 1 HNMR (600MHz, CDCl3 ): ı 8.2 (d,1H, Ar-H), 7.84(d,1H, Ar-H), 7.74 (m, 4H, Ar-H), 8.02 (s, 1H, Ar-H), 5.32 (d, 1H,
J = 15.4 Hz), 4.98 (d, 1H, J = 15.1 Hz) 3.67 (s, 6H, −OCH3), 7.02 (d, 1H, J = 8.0 Hz), 7.42 (d, 1H, J = 8.0 Hz); 13 C NMR assignments
13 C NMR (150 MHz, CDCl ) ı 184.2 ( C CO C), 196.2 ( C CO CH), 162.96 (C C), 160.27 (C C), 150.07 (C C), 126.22
3
(C C), 125.90 (C C), 121.40 (C C), 121.45 (C C), 127.18(C C), 134.03 (C C), 135.79 (C C), 150.82 (C C), 132.63 (C C),
130.70 (C C), 132.07 (C C), 137.51 (C C), 56.5( OCH3 ).

2.2. Computational details

All the calculations are performed using GAUSSIAN 09 suit of programs [22]. Density functional theory (DFT) method with
B3LYP and 6-311G** basis sets have been used for ground state geometry optimization of all compounds. The Berny algorithm
is default optimization algorithm included in Gaussian which is developed by Bernhard Schlegel [23]. This algorithm uses
the forces acting on the atoms of a given structure together with the second derivative matrix (called the Hessian matrix) to
predict energetically more favorable structures and thus optimize the molecular structure towards the next local minimum
on the potential energy surface. The B3LYP method is considered very reliable to reproduce the electronic geometries as it
has been applied to many combined experimental and computation studies [24–26]. All the geometries are confirmed as
minimum by calculating their analytical frequency. The parent compound 2 is used to test the efficiency of different DFT
methods for the calculation of second-(ˇ) and third-order polarizability () because it is often observed that B3LYP method
is found to overestimate the higher order polarizabilities. Fig. 1 shows ˇ and ␥ amplitudes for compound 2 using different
DFT methods including B3LYP, PBE0, BMK, M06 and CAM-B3LYP. A careful analysis of Fig. 1 indicates that as anticipated
B3LYP has slightly overestimated the ˇ and  amplitudes of compound 2 and CAM-B3LYP has shown lower values while
PBE0, M06 and BMK shows reasonable agreement with each other. We have chosen BMK method for further calculations of
NLO properties and spectroscopic properties of all compounds. This is because the BMK is already extensively studied for
coumarin based chalcone hybrids while its effectiveness is compared with other methods as well as to the experimental
values of transition energies of coumarin based chalcone hybrid derivatives [27]. The absorption and emission spectra are
calculated using TD-BMK/6-311G** level of theory. The solvent effects were considered using polarizable continuum model
(PCM) with acetonitrile and dioxane solvents for absorption and emission spectra, respectively, as in experiments.
For the calculation of second- (ˇ) and third-order polarizability (), a well-known finite field (FF) methodology combined
with BMK functional is applied in present study. In FF method, a static field is applied and total energy of the molecule is
expressed by following equation:
1 1 1
E = E (0) − 1 F1 − ˛ FF − ˇ FFF −  F F F F − . . . (1)
2 ij i j 6 ijk i j k 24 ijkl i j k l
here, E(0) denotes the total energy of the system in the absence of an electronic field while , ˛, ˇ and  are the vector
components of the dipole moment, the linear polarizability, NLO second and third-order polarizabilities, respectively. The i,
j, k label the x, y and z components, respectively. It can be seen from the above equation that differentiating E with respect
to F obtains the , ˛, ˇ, and  values. Here ˇ, and  values represent the origin of second-order (␹2 ) and third-order (␹3 )
nonlinear optical (NLO) susceptibilities, respectively.
8 S. Muhammad et al. / Optik 164 (2018) 5–15

Scheme 1. The rout for synthesis of compound 2.

The second-(ˇ) and third-order () polarizabilities are computed as:

3 
ˇi = ˇiii + ˇijj + ˇikk i, j, k = x, y, z (2)
5
     
ˇtot = ˇxxx + ˇxyy + ˇxzz + ˇyyy + ˇyzz + ˇyxx + ˇzzz + ˇzxx + ˇzyy (3)

While for average  amplitude

  1  
 = iijj + ijij + ijji . (4)
15
ij=x,y,z

These components are reduced to six at least for static third-order polarizability assuming Kleinmann symmetry.
  1   
 = xxxx + yyyy + zzzz + 2 xxyy + xxzz + yyzz . (5)
5
The components of ˇ and  amplitudes in terms of cartesian coordinates are computed using GAUSSIAN 09 [22].

3. Results and discussion

3.1. Synthesis

We have synthesized coumarin appended chalcone derivative, 2-[3-(2,4-Dimethoxy-phenyl)-acryloyl]-benzochromene-

3-one (2) by Claisen–Schmidt aldol condensation reaction strategy and Scheme 1 outlines the synthetic route for the synthesis
of the chalcone derivative. The structures of compounds were confirmed using IR, 1 H NMR and 13 C NMR techniques.

3.2. Molecular geometry and electronic spectra

The optimized molecular geometry of compound 2 ((E)-2-(3-(2,4-dimethoxyphenyl)acryloyl)-3H-benzo[f]chromen-3-

one) is showed in Fig. 2. The optimized compound 2 possesses planer geometry with 0.011 Å torsional angle among coumarin,
carbonyl and dimethoxy phenyl fragments (see Fig. 2 lateral view). A direct comparison of geometrical parameters is not
possible due to the lack of single crystal parameters for compound 2. Nevertheless, a planer structure with nearly zero torsion
angles is in accordance to the similar compounds (3-(3-(2-(thiophen-2-yl)thiophen-5-yl)prop-2-enoyl)-2H-1-benzopyran-
2-one) as reported by single crystal analysis [27]. The absorption spectrum of compound 2 is calculated in acetonitrile both
experimentally and theoretically. The experimental peak of maximum absorption wavelength as determined in acetonitrile
solution is 393 nm, which might be attributed to ␲ to ␲* transition. While on the other hand, the theoretically calculated
spectrum of compound 2 showed a HOMO to LUMO transition with oscillator strength of 1.226 at maximum absorption
wavelength of 392 nm, which is in a very good agreement to its experimental value (see Fig. 3). The overview of frontier
molecular orbitals (FMOs) as involved in transition indicates a moderate charge transfer from dimethoxyphenyl to coumarin
moieties through the ␲-conjugated bridge as shown in Fig. 3. Similarly, the emission spectrum has been determined exper-
imentally as well as calculated using TD-DFT optimization of excited state geometry of compound 2. The Fig. 4 shows the
experimental and theoretical emission spectra of compound 2 with emission values of 501 nm and 461 nm, respectively.
Both the peaks have slight shoulder peaks with reasonable agreement with each other. Both the absorption and emission
spectra indicate intermolecular charge transfer nature of compound 2.

3.3. Nonlinear optical response properties

Furthermore, we have performed DFT calculations to check the NLO response of compound 2 by calculating its static
second-order (ˇtot ) and third-order (<␥>) nonlinear polarizabilities, which are considered as the origin of second-order
and third-order susceptibilities, respectively. The compounds with good ˇ are considered as good contender for frequency-
doubling applications while a larger <␥> is considered as signature for two-photon absorption (TPA) process. The calculated
values of ˇ and <␥> amplitudes for compound 2 are given in Table 1.
A careful analysis of Table 1 shows that the ␤tot and <> amplitudes of compound 2 are 120.23 × 10−30 esu and
677.12 × 10-36 esu, respectively. The compound 2 possesses not only non-zero amplitudes of ˇtot and <> but also the
 S. Muhammad et al. / Optik 164 (2018) 5–15 9

Fig. 2. The optimized structure of compound 2 with top and lateral views.

Fig. 3. The experimental and calculated (TD-BMK/6-311G**) absorption spectra of compound 2 with picture of crucial orbitals involved in transition.

strength of these amplitudes is reasonably large. To perform a comparative analysis, we have also calculated the ˇtot and
<> amplitudes of para-nitroaniline (PNA) at the same BMK/6-311G** level of theory. The PNA is often considered as a proto-
type NLO molecule because many reports highlight the comparison of NLO response of a newly designed compound with that
of PNA to show its merit of figure in NLO applications. The ˇtot and <> amplitudes of PNA are found to be 21.20 × 10−30 esu
and 34.08 × 10-36 esu, which are ∼6 and ∼20 times larger than those of PNA at BMK/6-311G** level of theory. These results
show a good NLO response of compound 2 for second- and third-order NLO applications.
10 S. Muhammad et al. / Optik 164 (2018) 5–15

Fig. 4. The experimental and calculated (TD-BMK/6-311G**) emission spectra of compound 2.

Table 1
The calculated values of second- and third-order NLO responses ˇtot (×10−30 esu) and <␥> (×10-36 esu) along with their individual components as for
compound 2 at BMK/6-311G** levels of theory.

ˇ Components  Components

␤xxx 0.18 ␥xxxx 2.443

␤xxy 0.72 ␥yyyy 50.299
␤xyy −0.43 ␥zzzz 3068.6
␤yyy −4.48 ␥xxyy 2.6672
␤xxz −0.66 ␥xxzz 11.877
␤xyz −2.36 ␥yyzz 117.6
␤yyz 5.14 <␥> 677.12
␤xzz −4.56 <␥> (PNA)a 34.08
␤yzz 47.16 – –
␤zzz 107.54 – –
␤tot 120.23 – –
␤tot (PNA)a 21.207 – –
a
The ␤tot and <␥> for para-nitroaniline (PNA) are also calculated at BMK/6-311G** levels of theory.

3.4. Substitution effect on NLO response

To further tune the above reported NLO response of compound 2 and to get more insights into the structure NLO prop-
erty relationship, we have designed more derivatives of compound 2 as 2a, 2b, 2c and 2d. All the molecular structures
adopted in derivatives are presented in Scheme 2 along with their cartesian coordinate axis. The compound 2, (E)-2-(3-
(2,4-dimethoxyphenyl)acryloyl)-3H-benzo[f]chromen-3-one, is taken as parent compound because we have indigenously
synthesized it in our laboratory. For detail synthesis, please see experimental section. The ortho and para methoxy groups
of parent compound 2 are replaced with OH, CH3 , NH2 and N(CH3 )2 groups to design compounds 2a, 2b, 2c and 2d, respec-
tively. It is important to mention that in our previous study, we have already investigated the effect of position and number
of methoxy groups on phenyl ring for NLO properties of different chalcone derivatives [18]. It has been found that para-
methoxyphenyl group was more efficient than the ortho- and meta-phenyls as electron donor moiety in chalcone derivatives.
In present investigation, we have designed the compounds to tune the electron donor moiety of coumarin-appended
chalcones as shown in Scheme 2.
We have calculated the second- and third-order NLO properties for all the derivatives and these are presented in
Tables 2 and 3, respectively, along with their parent compound 2. We would like discussing these results explicitly for
 S. Muhammad et al. / Optik 164 (2018) 5–15 11

Scheme 2. The schematic presentation of derivatives of compound 2.

Table 2
The calculated values of second-order polarizabilityˇtot (×10−30 esu) along with its individual components for compounds 2, 2a, 2b, 2c, and 2d at BMK/6-
311G** levels of theory.

ˇ 2 2a 2b 2c 2d

␤xxx 0.18 0.03 −0.03 −0.19 −1.49

␤xxy 0.72 −0.05 −0.08 0.16 0.71
␤xyy −0.43 −0.15 −0.42 0.23 0.32
␤yyy −4.48 −4.22 −2.14 −4.15 −7.72
␤xxz −0.66 0.50 0.03 1.88 −1.43
␤xyz −2.36 0.86 −0.21 −5.10 −3.89
␤yyz 5.14 −3.66 5.91 14.89 4.48
␤xzz −4.56 2.81 4.02 −18.85 −11.30
␤yzz 47.16 34.68 37.76 72.29 72.71
␤zzz 107.54 91.37 37.62 190.29 303.43
␤tot 120.23 93.34 56.34 218.84 313.68
a 5.67 4.40 2.65 10.31 14.79
a
The  is ratio of ␤tot amplitudes of each compound with ␤tot of PNA.

Table 3
The calculated values of third-order polarizability␥ (×10−36 esu) along with its individual components as for compounds 2, 2a, 2b, 2c, and 2d at BMK/6-
311G** levels of theory.

␥ 2 2a 2b 2c 2d

␥xxxx 2.443 0.718 2.000 1.399 9.605

␥yyyy 50.29 2512 85.38 59.07 67.07
␥zzzz 3068. 46.94 1855 4439 7033
␥xxyy 2.667 2.635 3.497 3.741 7.486
␥xxzz 11.87 1.714 7.246 23.71 25.98
␥yyzz 117.6 114.6 241.4 212.7 199.8
<␥> 677.1 559.7 449.4 996.0 1515
a 19.84 16.42 13.18 29.22 44.45
a
The  is ratio of <␥> amplitudes of each compound with <␥> of PNA.

second- and third-order NLO responses. Concerning the second-order NLO polarizability, the Table 2 shows a significant
increase in the amplitude of ˇtot as one goes from parent compound 2 to 2c and 2d, while a decrease in ˇtot amplitudes for
derivatives 2a and 2b which might be attributed to the superior and poorer push-pull combinations in derivatives, respec-
tively, as compared to their parent compound 2. The calculated ˇtot amplitudes of compounds 2c and 2d are 218.84 × 10−30
and 313.68 × 10−30 esu, respectively, which are ∼2 and ∼3 times larger than parent compound 2 while ∼10 and ∼15 times
larger than that of PNA. This comparison shows a significant effect of substitution on compound 2, which may bring forth
novel compounds with efficient NLO response properties like as in derivatives 2c and 2d.
Similarly, the third-order NLO response properties of derivatives 2a to 2d are collected in Table 3 along with their
parent compound 2. A similar but more pronounced substitution effect is also evident from the calculated amplitudes of
2a to 2d. The derivatives 2a, 2b, 2c and 2d show calculated <> amplitudes of 559.7 × 10−36 , 449.4 × 10−36 , 996.0 × 10−36
and 1515 × 10−36 esu, respectively. In line with above amplitudes, the derivatives 2a and 2b showed a decreasing while
derivative 2c and 2d indicated an increasing effects in their respective <> amplitudes. A careful analysis of Table 3 indicates
12 S. Muhammad et al. / Optik 164 (2018) 5–15

Table 4
The transition energies (E), oscillator strength (fo ), transion moment (␮ng ), % configuration interaction (C.I.) and change in dipole moments between
ground and crucial excited states (␮ng ) for all compounds at TD-B3LYP/6-311G** level of theory.

Sys. Electronic Excitation E (eV) fo ␮ng Transition %C.I. ␮ng

2 S0 → S1 3.160 1.225 3.978 H→L 63 0.555

2a S0 → S1 3.232 1.199 3.891 H→L 61 0.203
2b S0 → S1 3.286 1.087 3.670 H→L 67 0.976
2c S0 → S1 2.889 0.993 3.746 H→L 67 4.859
2d S0 → S1 2.766 0.953 3.745 H→L 67 4.881

that derivatives 2c and 2c possess ∼1.5 and ∼2 times larger than parent compound 2 while ∼29 and ∼44 times larger than
that of PNA.

3.5. TD-DFT calculations

To probe the origin of second- and third-order NLO response, we have performed the TD-DFT calculations for all 2 to
2d compounds as given in Table 4. Usually, as in several previous investigations,[28,29] the spectroscopic parameters are
applied to see the origin of NLO response by considering simple two- and three-states approximations based on perturbative
formula for static longitudinal ˇL and  L values, respectively [30].

2
0ng
ˇL = 3ng (6)
E

⎡ ⎤
2
2ng ng 4ng 2ng 2mn
L = 24 ⎣ 3
− 3
+ 2 E
⎦ (7)
E ng E ng Eng mg
m(m =
/ n)

where ng , E and are transition moment, transition energy and change in dipole moment related with transition
from ground (|g) to crucial excited (|n) state while ␮mn is the transition moment between mth and nth excited states. These
so called two- and three-states approximation are widely applied in theory and experiments to explain the changes in higher-
order polarizabilities (␤ and ). For further details of above approximations we refer the reader to the work of Bredes et al.
[31], Nakano et al. [32] and similar others [30,33–35]. For present investigation, the spectroscopic parameters are calculated
with TD-DFT method at BMK/6-311G** level of theory. The Eqs. (6) and (7), show that the transition moment, oscillatory
strength and change in dipole moment terms are in nominator while the transition energy term is in the denominator
which denotes that a chemical compound with lower transition energy and larger transition moments and/or oscillatory
strengths along with the change in dipole moments is expected to have larger ␤ and  amplitudes. The calculated values of
fo , ng , E ng and ng are collected in Table 4, which indicates that derivatives 2c and 2d possess lower transition energies
and larger change in dipole moments between ground and excited states as compared to those for other derivatives and
parent compound 2. Obviously, these two parameters play crucial role to enhance the NLO response of derivatives 2c and
2d. While the third term ng does not show a dominant contribution because of its slight variation among all the derivatives.

3.6. Frontier molecular orbital (FMOs) analysis

In order to see the nature of charge transfer among all adopted compounds, we have drawn their frontier molecular
orbitals as involved in crucial transitions in Table 4. All the FMOs are collected in Fig. 5, which include HOMOs and LUMOs
only because the crucial lowest energy transitions involve only these orbitals. FMOs provide very vital information about
the reactivity as well as nature of intramolecular charge transfer characteristics of a compound. An attentive analysis of
Fig. 5 shows that the nature of intramolecular charge transfer is moderate and similar for 2a and 2b while compounds 2, 2c
and 2d indicate a significant transfer of charge from substituted phenyl groups to coumarin appended chalcone fragments.
It is possible to assign an order of increasing strengths of donor groups OH < Me < MeO < NH2 < NR2 on phenyl moiety of
above titled coumarin appended hybrid chalcones. Additionally, we have also calculated the HOMO-LUMO orbital energy
gaps (EH-L ) for all compounds. The EH-L values of compounds 2, 2a, 2b, 2c and 2d are found to be 4.412, 4.532, 4.706,
4.032 and 3.824 eV, respectively, at BMK/6-311G** level of theory. Among all the compounds, the compound 2d illustrated
the lowest EH-L value, which is also justifying the lowest energy transition in compound 2d. A further analysis of orbitals
energies for HOMOs of all compounds indicate that HOMO of compound 2d significantly stabilized as compared to those
other compounds, which perhaps results in lower EH-L values, lower transition energy as well as larger NLO response
properties as explained in two- and three-states approximations.
 S. Muhammad et al. / Optik 164 (2018) 5–15 13

Fig. 5. The FMOs of all chemical compounds as studied in present investigation.

Fig. 6. The molecular electrostatic potentials (MEPs) for all compounds with iso-value of 0.020 a.u., where negative potential decreases in order of
red > orange > yellow > green > blue. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)

3.7. Molecular electrostatic potentials (MEPs)

In order to get more insights about structure-property in our designed compounds, we have generated the molecular
electrostatic potential maps for all systems in present investigation (see Fig. 6). The MEPs provide very important information
in the form of local potentials on the total density surface of a molecule. The potentials are represented in the form of color
codes where a red color illustrates the maximum negative potential and a blue color indicates a maximum positive potential
while yellow, green and orange colors highlight different ranges of mixed positive and negative potentials. A careful analysis
of Fig. 6 indicates that MEPs for all the chemical systems are somewhat similar patterns where significant negative potentials
are present in the center due to the C O bonds and slightly positive potentials in the form of green area are visible laterally.
It is expected from the negative potential sites that an electrophile may attach the C O bond while the other positions
are quite stable. There is no significant positive potential for any derivative except compound 2a which is due to its acidic
14 S. Muhammad et al. / Optik 164 (2018) 5–15

hydrogen atoms. The compound 2a not shows positive potential on lateral sides but also the central negative potential is
the lowest among all compounds. The absence of a clear positive potentials in all derivatives (except compound 2a) may be
advantage for more stability and less probability of further nucleophilic reactions.

4. Conclusions

In the framework of above dual approach comprising of experimental and quantum computational techniques, following
conclusions can be made as under:

1 The first synthesis and characterization of compound 2 is reported experimentally.

2 The experimental and theoretically calculated absorption and emission spectra showed peaks at 392 and 461 nm, which
are found to be in agreement with their experimental peaks at 393 and 501 nm, respectively.
3 The calculations of NLO response properties indicated that the ˇ and <␥> amplitudes of compound 2 are ∼6 and ∼20 times
larger that those of PNA at BMK/6-311G** level of theory, indicating a good potential of our indigenously synthesized
compound 2 for NLO applications.
4 A structure-property relationship has been explored by performing the substitutions of donor groups in the form of further
four derivatives i.e. 2a, 2b, 2c and 2d. Interestingly, among these derivatives, the derivative 2d shows robust NLO response
with its ˇ and <␥> amplitudes as large as 218.84 × 10−30 esu and 1515 × 10-36 esu, respectively.
5 Thus, we have reported the first synthesis of compound 2 as well as explored the potential of compound 2 and its derivatives
as efficient NLO-phores.

Acknowledgement

This article contains the results and fundings of a research project that is funded by King Abdulaziz City for Science and
Technology (KACST) Grant No. .

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