Synthesis, Spectroscopic, SQUEEZE method/XRD

interactions, linear and Nonlinear Optical properties,

and antibacterial effect of the ligand/copper(II)
complex tetradentate Schiff base: Experimental and
Theoretical Studies
Naouel Boudraa
University of Mentouri Brothers
Rachida Assabaa
University of Mentouri Brothers
Nadir Ghichi

University of Mentouri Brothers

Meriem Zaidi
University of Setif-1
Douniazed Hannachi
University of Setif-1
Amel Djedouani
Ecole Normale Superior Assia Djebar of Constantine, University
Ahmed Abderrahim Yahiaoui
Higher Normal School of Technological Education (ENSET) Skikda
Helen stoeckli-evans
University of Neuchatel

Research Article

Keywords: Schiff base, Copper, Antibacterial, optical properties, DFT and TD-DFT

Posted Date: March 18th, 2024

DOI: https://doi.org/10.21203/rs.3.rs-4080351/v1

License:   This work is licensed under a Creative Commons Attribution 4.0 International License.
Read Full License
Additional Declarations:
No competing interests reported.

Tables 1 to 8 are available in the Supplementary Files section

Synthesis, Spectroscopic, SQUEEZE method/XRD interactions, linear and Nonlinear Optical properties, and
antibacterial effect of the ligand/copper(II) complex tetradentate Schiff base: Experimental and Theoretical
Studies

Naouel Boudraaa,b, Rachida Assabaaa, Nadir Ghichic,*, Meriem Zaidid, Douniazed Hannachid,e, Amel Djedouanif,g,
Ahmed Abderrahim Yahiaouih, Helen stoeckli-evansj

a
Chemistry Department, University of Mentouri Brothers, Constantine 1, Algeria

b
Biotechnology Research Center-C.R.Bt-Constantine Algeria

c
Unit of Research CHEMS, University of Mentouri Brothers, Constantine 1, Algeria

d
Department of Chemistry, Faculty of Sciences, University of Setif-1, Setif, Algeria

e
Laboratory of Electrochemistry, Molecular Engineering and Redox Catalysis (LEIMCR), Department of Basic
Education in Technology, Faculty of Technology, Ferhat Abbas University, Setif-1, Algeria; Department of Chemistry,
Faculty of Material Sciences, University of Batna-1, Algeria

f
Ecole Normale Superior Assia Djebar of Constantine, Department of Physics and Chemistry, University Constantine 3,
250 0 0, Algeria

g
Laboratory of Analytical Physicochemistry and Crystallochemistry of Organometallic and Biomolecular Materials,
University Constantine 1, 250 0 0, Algeria

h
Higher Normal School of Technological Education (ENSET) Skikda, Algeria

i
Institute of Physics, University of Neuchatel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland

*Corresponding author. E-mail address: nadirgh82@hotmail.com ; phone:(+213) 0656 205 038

Abstract

This study focuses on the synthesis, characterization, and biological evaluation of a novel N 2O2 donor Schiff base
ligand: N,N'-bis(2-hydroxypropiophenone)-1,2-ethanediamine L and its’ copper(II) complex CuL Extensive
spectroscopic methods including 1H and 13
C NMR, FT-IR, Raman and UV-Vis spectroscopy were employed for the
detailed characterization of these compounds. The structure of the CuL complex was elucidated using single-crystal X-
ray crystallography, employing the SQUEEZE procedure in PLATON to resolve refinement issues. The antibacterial
efficacy of the synthesized compounds was assessed using the disc-diffusion method against a range of bacteria:
Staphylococcus aureus, Bacillus cereus (Gram-positive), and Escherichia coli, Pseudomonas aeruginosa, Klebsiella
pneumoniae (Gram-negative). Additionally, the study extends to the computational realm, where Density Functional
Theory (DFT) and Time-Dependent-DFT (TD-DFT) methods were utilized to analyze the structural optimization,
optical properties, and both static and dynamic hyperpolarizabilities of CuL and its analogues with nickel (NiL) and
zinc (ZnL). The findings contribute valuable insights into the spectral properties, crystal structure, and biological
activities of these Schiff base complexes.

1
Keywords: Schiff base; Copper; Antibacterial; optical properties; DFT and TD-DFT

1. Introduction

Schiff base ligands have been widely studied for their ease of synthesis using the condensation reaction of primary
amines with carbonyl compounds. These ligands can coordinate with most transition metal ions to form complexes. The
azomethine nitrogen of Schiff bases is primarily responsible for coordinating with transition metals [1]. Although
discovered in coordination chemistry almost 100 years, Schiff bases represent a key role as ligands which are among the
most commonly utilized organic substances [2]. According to the literature, the complexes of Schiff base complexes
contains several properties in various fields, such as medical (antibacterial [3]-anticancer [4]-antifangic [5]), industrial
(anticorrosion [6]). Copper is well known as bioessential element, the role played by this ion in the active sites of a
large number of metalloproteins has stimulated efforts to design and characterize copper complexes as models for a
better understanding of biological systems [7], Copper complexes of ligands containing imine moieties have found
countless applications [8].

In the present investigation we describe the synthesis, characterization of N 2O2 schiff base ligand L derived from 2-
hydroxypropiophenon and their nickel CuL complex, the prepared ligand was characterized by spectral methods ( 1H
and 13C NMR, FT-IR, RAMAN, UV-visible), Single crystal X-ray analysis of the complex have been carried out, and
all the synthetized compounds have been tested for their antioxidant activities. On the other hand, Density Functional
Theory (DFT) and time-dependent-DFT (TD-DFT) calculations have been recognized as profoundly efficacious
methodologies for the prediction and design of novel materials characterized by superior optical attributes. Therefore,
the aim of this study is to explore the influence of transition metals on stability, absorption spectrum, and nonlinear
optical (NLO) responses in copper ligand complexes (CuL) and its analogues, specifically those incorporating nickel
(NiL) and zinc (ZnL).

2. Experimental

2.1. Materials and methods

All the chemicals and solvents were purchased from, Sigma Aldrich and were used without further purification.
Melting points were determined on a Kofler melting point apparatus and are uncorrected. The infrared spectra of the
synthesized products were recorded in ATR mode on Agilent cary 600 FTIR Spectrometer in the range 400-4000 cm-1.
The RAMAN spectra were recorded on a thermo Scientific DXR Raman spectrometer in the range 0-3500 cm-1.
Electronic spectra were recorded at room temperature, as DMSO solutions using Agilent cary 60 UV-Vis spectrometer,
in the range 200-800 nm. The NMR spectra were recorded on a Bruker Avence DPX 250MHz spectrometer 250 for 1H
and 13C.

2.2. XRD and HSA computing details

Data collection: Bruker D8 Venture diffractometer; program used to refine structure: SHELXL2018/3 [9]; molecular
graphics: Mercury [10]; software used to prepare material for publication: PLATON [11], SHELXL2018/3 [9]. Crystal
data, data collection and structure refinement details are summarized in Table 1 and selected geometric parameters are
presented in Table 2. Atoms C15, C16 and C17 of the central bridge of the ligand were refined as disordered with a
refined occupancy ratio of 0.715(6):0.285(6).

2
A region of disordered electron density, occupying voids in the unit cell of ca 233 Å3 for an electron count of 111, was
removed with the SQUEEZE procedure in PLATON [12]. This followed unsuccessful attempts to model it as a
plausible solvent molecule. The stated formula mass, density, etc. do not include the disordered solvent.

The C-bound H-atoms were included in calculated positions and treated as riding atoms: C-H = 0.95 - 1.00 Å with
Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H-atoms.

2.3 Screening for antibacterial activity

The in vitro antibacterial screening of the schiff base ligand L and the corresponding metal complexe, have been carried
out against gram-positive (Staphylococcus aureus ATCC25923; Bacillus cereus ATCC 10876) and gram-negative
(Escherichia coli ATCC25922; Pseudomonas aeruginosa ATCC27853; Klebsiella pneumonia ATCC 13883) using the
common disc diffusion method. The inoculum used was standardized to an absorbance between 0.08 and 0.1, read at
625 nm, equivalent to 108 UFC/mL. The inoculums suspension of the bacterial stains was swabbed on the entire surface
of agar media. The discs, previously prepared and impregnated with a 10 µl dose of the tested compounds, were then
transferred to the inoculated dishes. The control discs were impregnated with 10 μL of DMSO (negative control).
Antibiotics were used as positive controls. The dishes were then incubated for 24 hours at 37°C. After incubation, the
absence of microbial growth results in a translucent halo around the disc, identical to sterile agar, whose diameter is
measured and expressed in millimeters. Antimicrobial activity is considered positive from a diameter greater than 6
mm. It is evaluated in this work as follows [2,13]:
-Very Strong activity: diameter ≥20 mm
-good activity: diameter between 16-20 mm
-medium activity: diameter between 11-15 mm
-low activity: diameter ≤ 10 mm.

2.4. Computational details

In this investigation, Density Functional Theory (DFT) calculations were executed through the utilization of the
Gaussian 16 software. These calculations were grounded in the X-ray crystallographic molecular structures of CuL
complex. The geometries of ML complexes, with M representing Ni, Cu and Zn were subjected to optimization using
the ωB97XD level of theory (is a range-separated version of Becke's 97 functional with additional dispersion correction
[14-15]. The basis set of 6-311+G** was utilized for the atoms H, N, C and O, whereas SDD basis set with the Stuttgart
Dresden effective core potentials to account for scalar relativistic effects were retained for transition metal.

Chemical reactivity analysis is founded on DFT and utilizes a functional Taylor expansion of energy. This approach
introduces multiple reactivity descriptors derived from energy derivatives with significant chemical implications [16].
By employing a finite difference approximation and Koopman's theorem [17-19], one can determine the electronic
chemical potential (µ) and global hardness (η) based on the energies of the frontier orbitals, HOMO and LUMO. The
reactivity indices, specifically chemical hardness and electronic chemical potential, for paramagnetic systems were
computed through the application of the subsequent mathematical
formulations ; [20-24]

(1)

3
 (2)

η = εL˗εH (3)

Chemical hardness (η) signifies a compound’s stability by gauging its resistance to electron transfer, while the
chemical potential (μ) characterizes the propensity for electrons to escape from the equilibrium system.
The global electrophilicity index (ω), introduced by Parr et al. [25] quantifies the ability of compounds to receive
electrons from the surroundings, as defined by:
(4)

The nonlinear optical (NLO) response and the absorption spectra of the studied compounds were calculated using the
DFT and TD-DFT methods.
The average polarizability (α) and its anisotropy (Δα) are described by the following relations :[26]

1
𝛼 = 3 (𝛼𝑥𝑥 + 𝛼𝑦𝑦 + 𝛼𝑧𝑧 ) (5)

The average first hyperpolarizability was calculated using the following formula : [26-27]

(7)

Where the components and are defined as:

1 𝑥,𝑦,𝑧
𝛽𝑖 = 𝛽𝑖𝑖𝑖 + 3 ∑𝑗≠𝑖 (𝛽𝑖𝑗𝑗 + 𝛽𝑗𝑖𝑗 + 𝛽𝑗𝑗𝑖 ) (8)

The components of second hyperpolarizabilities are given by [28-30]

1
𝛾𝑖 = 15 ∑𝑗,𝑘(𝛾𝑗𝑗𝑘𝑘 + 𝛾𝑗𝑘𝑘𝑗 + 𝛾𝑗𝑘𝑗𝑘 ) , i, j= {x, y,z} (9)

The average of is measured as:

(10)

The hyper-Rayleigh scattering (HRS) technique encompasses the detection of the incoherent scattering second
harmonic generation at frequency 2ω when illuminated by a laser of frequency ω. Within HRS, it is possible to
determine the first hyperpolarizability βHRS and its depolarization ratios DR, through the relation:[27,31]

4
 2ω; ω,ω (11)

where 〈β²ZZZ〉 and 〈β²XZZ〉 are orientational averages of the β tensor without assuming Kleinman's
conditions.[32]

The depolarization ratios (DR) provide insights into the geometric characteristics of the chromophore, which constitutes
the component of the compound responsible for the NLO response (in an ideal one-dimensional donor/acceptor system
DR = 5, while for an octupolar molecule, DR = 1.5)

⟨𝛽 2 ⟩
𝐷𝑅 = ⟨𝛽𝑍𝑍𝑍
2 ⟩
(12)
𝑋𝑍𝑍

3. Synthesis and crystallization

3.1. Synthesis of ligand L: ( N,N'-bis(5-bromosalicylaldehyde)-1,2-propanediamine)

To a solution of 1,2-diaminopropane (0.15 g, 2 mmol) in (05 ml) of absolute ethanol was added a solution of 5-bromo-
2-hydroxybenzaldehyde (0.80 g, 4 mmol) in absolute ethanol (30 ml), the mixture was refluxed for 2 h. The yellow
precipitate was filtered, and recrystallized from EtOH. Yeld, 0.36g (42%), melting point 120°C. FT-IR, ν (cm-1): 1629
(C=N), 2840 (O-H), 1567(Ar.C=C), 1280 (C–O), 558 (C-Br). Raman ν (cm-1): 1635 (C=N). UV-Vis (λmax
(nm),DMSO): 325,414. NMR spectroscopy. Ligand L was characterized by its 1H NMR spectrum, which exhibited
several diagnostic signals. 1H NMR (250 MHz, CDCl3): 1.42 (d, J = 6.0 Hz, 3H, CH3), 3.94-3.69 (m, 3H, CH2, CH),
6.86 (dd, J = 8.6, 1.9Hz, 2H, HAr), 7.41-7.36 (m, 4H, HAr), 8.26 (s, 1H, CH=N), 8.30 (s, 1H, CH=N), 13.25 (s. 2H, OH).
13
C NMR (62.9MHz, CDCl3) : 165.30 ; 163,43 ; 160,15 ; 160,09 ; 135,23 ; 135,17 ; 133,68 ; 133,65 ; 119,98 ; 119,12 ;
119.09 ; 110.27 ; 110.24 ; 65.74 ; 65.08 ; 20.43.

3.2. Synthesis of complex CuL

The copper complex was prepared by stirring methanolic solutions of the ligand (0.21g, 0.5 mmol) in methanol 10ml,
and copper chloride(0.06g, 0.5mmol) in 2ml of methanol at room temperature for 1 hour, the complex was filtered and
recrystallized from the mixture (CH2Cl2/ MeOH) (2:1). Yeld 0.09g (39%). melting point >266°C. FT-IR, ν (cm-1): 1627
(C=N), 1304 (C-O), 427 (Cu-N), 576 (Cu-O). Raman ν (cm-1): 1645 (C=N), 515 (Cu-O), 210 (Cu-N). UV-VIS, λmax
(nm) : 370,600. 1H NMR (250 MHz, CDCl3): 2.1 (d, 3H, CH3), 3.1-4.1 (m, 3H, CH2, CH).

4. Results and discussion

4.1. Spectroscopic studies

4.1.1. FT-IR spectral studies

The infrared spectra of the free Schiff base ligand (Fig.1) reveals bands at 1629 cm-1 for L, that are assigned to imine
stretching modes [33,34], in the copper complexe these band shifted to lower values 1627 cm -1, this shift is due to the
reduction of the double bond character of the C=N bond [35], owing to the coordination of the ligand to metal ions via
the nitrogen of the azomethine group [36-37]. The band of the free O–H stretching vibration was not found in the free
ligand spectra, this can be explained by the formation of intra-molecular hydrogen bond [38], instead a weak band was
observed at near 2840 cm-1 for ligand L, this band can be assigned to internally hydrogen bonded O–H stretching
vibrations [39-41]. The C=C band vibration of phenyl rings of the free ligand appear at 1567 cm -1 for L [42]. The
5
frequency of C–O phenolic stretching vibration of ligand L at 1280cm-1 displaced to higher frequency 1304cm-1 on
coordination, [38,43], the displacement was slightly for lower wavenumber 1221 cm -1 [43,44]. In the ligand L the
stretching vibration of the C-Br band is observed as a medium band at 558 cm -1 [45]. The frequencies of metal-ligand
bands are generally expected in the range 400-600 cm-1 [46]. These bands are usually weak and difficult to locate [47].
In the copper (II) complex we have assigned bands at 427 cm -1 and 576 cm-1 to copper nitrogen and copper oxygen
vibrations respectively [48-49].

4.1.2 Raman spectral studies

The Raman spectra of the complexe was compared to the spectra of their corresponding ligand (Fig.2). The C=N
stretching vibration of schiff base L appear at 1635 cm -1 [50], after coordinaton it shifted to 1645 cm -1 . This shift to
higher or lower wavenumber could be explained by the change of the electronic density of the imine bond, caused by
coordination through the nitrogen atom. The metal-ligand vibration is characteristic to the complexes, in copper
complex we have assigned bands at 515 cm-1 and 210 cm-1 to Cu-O and Cu-N respectively [51-52].

4.1.3 Electronic spectra

The UV-Vis absorption spectra of the Schiff base ligand L (Fig.3) exhibits absorption band in the region 300- 350 nm,
according to the literature this band is assigned to the n→ π* transition of the azomethine groupe [53]. The band at the
region 400-450nm can be attributed to intramolecular charge transfer interactions [54-56]. The copper complex shows a
band centered at 370nm, due to ligand to metal charge transfer LMCT [57]. The broad and weak band in the 600 region,
corresponds to the d-d electronic transition, and is consistent with the square planar geometry of Cu(II) complexes [58-
59].

4.1.4. 1H. And 13C. NMR spectroscopy of Ligand L

The 1H NMR spectrum of the ligand (Figs. S2,S3,S4) was characterized by several interesting signals. We observe the
appearance of two signals corresponding to the CH 3 and CH2-CH groups, one in the form of a 3H integration doublet at
1.41 ppm with a coupling constant J = 6.0 Hz, corresponding to the CH3 group, and the other in the form of a 3H
integration multiplet between 3.94 ppm and 3.69 ppm corresponding to the CH 2 and CH groups. The two 1H integration
singlets were detected at δ = 8.26 ppm and δ = 8.30 ppm, corresponding to the two protons of the CH=N groups. A
singlet 2H integration was detected at δ = 13.25 ppm, corresponding to the protons of two phenols. Finally, the aromatic
proton signals resonate as a doublet of 2H integration doublets at δ = 6.86 ppm, with coupling constants J = 8.6 and 1.9
Hz, and four protons were observed in the region from 7.41 to 7.36 ppm, exhibiting a multiplet pattern.

The 13C NMR spectrum (Fig. S5) is characterized by the presence of the following signals: The carbons of the aromatic
cycle carrying the OH function appear as signals at 160.15 ppm and 160.09 ppm, and those carrying the bromine appear
as signals at 110.27 ppm and 110.24 ppm. The remaining aromatic carbons appear within the usual range of 135.23 to
119.09 ppm. Carbons bonded to nitrogen with a double bond are observed at 165.30 ppm and 163.43 ppm. The carbons
of the methyl groups are detected around 20.43 ppm, while the carbons of the CH 2 and CH groups are observed at 65.74
ppm and 65.08 ppm, respectively.
4.1.5. 1H and 13C. NMR spectroscopy of complex CuL

6
Regarding the proton and carbon-13 NMR spectrum of the complex, a subtle shift in chemical displacement values is
noted, along with the absence of protons from the two hydroxyl groups in the proton NMR spectrum, signaling the
formation of the complex.

4.2. Crystal and molecular structure of CuL

Compound CuL (Fig. S1 and Scheme))crystallized in the monoclinic space group I2/a. (see Table 1). The ligand
coordinates to the copper(II) atom in a tetradentate manner. Atom Cu1 has a four-fold coordination sphere, CuN2O2,
with a square planar geometry and a t4 value of 0.06 [60] [extreme forms 0.00 for square-planar and 1.00 for
tetrahedral and 0.85 for trigonal planar]. As illustrated in (Fig. 4), the central bridge of the ligand, (-CH2--CH(CH3)-;
atoms C15, C16 and C17) is disordered about a pseudo two-fold rotation axis that bisects the copper atom. Selected
bond lengths and bond angles involving the atom CuL are given in Table 2. The aromatic rings (C1-C6 and C8-C13)
are inclined to each other by 6.0(2)°.

In the crystal, complex molecules stack in columns along the b-axis direction. Complex molecules related by an
inversion center (symmetry operation -x – 0.5, -y – 0.5, -z – 0.5) have a Cu···Cu separation of 3.379 Å, while those
displaced along the b-axis (symmetry operation x, y – 1, z) are separated by 3.736 Å. There are two short C-H…O
interactions present involving inversion related molecules (Table 3). A view of the crystal packing illustrating the voids
occupied by the disordered solvent molecules is shown in (Fig. 5).

4.3 Antibacterial activity evaluation

The inhibition effects of the complexe and the free Schiff base were evaluated against five bacterial strains, including
two gram-positive: S.aureus, B.cereus and three gram-negative strains: E.coli, P.aeruginosa, K.pneumonia using
Amoxicillin, gentamicin and penicillin) [61] as positive controls and solvent DMSO as a negative control, the results
are represented in Table 4. the screening data indicate that, the tested compounds did not exhibit any inhibitory effect
against all the tested bacterial strains except the ligand L, that showed good activity against B.cereus, and weak activity
against E.coli, P.aeruginosa, K.pneumonia, S.aureus. Comparing to penicillin, ligand L exhibited better activity against
positive E.coli, P.aeruginosa and negative S.aureus.] These observations are similar to earlier reports [61,62-63] of
antibacterial activities of tetradentate N2O2 Schiff bases. In disc diffusion method the diameter of the inhibition zone is
related to the sensitivity of the isolate and to the diffusion rate of the drug through the agar medium [64]. Diffusion rate
of chemical compounds on agar plates may be affected by other factors as: solubility, dipole moment, molecular mass
and hydrophobicity [65]; Additionally, chemicals structure might influence their antibacterial activities [66], generally,
the electronic nature (electron withdrawing and electron releasing) and position of substituents of the phenyl ring
determines the antimicrobial activities [67], studies of structure activity relationship revealed that the presence of
electron-withdrawing group Br on the para position of the phenyl rings has a positive effect on the antibacterial activity
[68].
4. DFT and TD-DFT studies

The geometries of complexes CuL, NiL and ZnL were DFT-optimized by the wB97XD/SDD/6-311G ** Method and
are illustrated in (Fig. 6), whereas calculated bond lengths and angles of ML (M = Cu, Ni and Zn) are summarized in
Table 5. In given complexes ML, the M(II) metal center is square-planar coordination surrounded by the ligand (L). For
example, the calculated Cu–N1, Cu–N2, Cu–O1, Cu–O2, Cu–C1 and Cu–C2 bond lengths for the L are 1.976, 1.960,

7
1.922, 1.922, 3.295 and 3.311 Å, respectively. The calculated geometries of CuL indicate a high level of agreement
with the experimental data concerning bond lengths and bond angles. Additionally, the comparison between DFT
optimized and XRD structures was performed by atom-by-atom superimposition of complex CuL (Fig.7) displays
notable agreement, and the value of root-mean-square error is 0.145 Å.
4.2 Reactivity indexes

The calculated reactivity indexes, including the electronic potential (µ) and global hardness () have been listed in
Table 6. The results indicate that the chemical hardness of the CuL complex (3.596 eV) is lower relative to those of the
NiL and ZnL complexes (3.617, 3.689 eV) respectively. This value implies that ZnL complex is comparatively less
reactive and more stable than the other complexes. The investigation into electron donation capacities, through the
chemical potential (electronegativity), reveals that the complexes NiL, ZnL, and CuL present closely aligned values (-
4.064, -3.994, and -3.943 eV, respectively), evidencing slight discrepancies. Such data suggest a progressive reduction
in the ability to donate electrons from CuL to ZnL, and subsequently to NiL. Consequently, it may be deduced that CuL
demonstrates an enhanced propensity for electron donation, potentially enhancing its reactivity in electron transfer
reactions and its interactions with a variety of chemical entities.

On the other hand, the analysis of the determined thermodynamic parameters at 298.15 K demonstrates a minimal
impact of the metal on both the molar heat capacity CvNiL≈CvCuL≈CvZnL = 82 Cal/Mol. -Kelvin) and the entropy
(SniL≈SCuL≈SZnL = 161 Cal/Mol. -Kelvin). The enthalpy (H) and Gibbs energy (G) of the studied complexes exhibit the
following order: ZnL < CuL < NiL. This ordering suggests that among the three complexes analyzed, ZnL exhibits the
lowest values of enthalpy and Gibbs free energy (see Table 6).

4.3 TD-DFT

The calculated results of absorption spectra parameters using TD-DFT, which include excitation energy (E, eV),
wavelength (, nm) and oscillator strength (f), and information about orbital transitions, can be found in Table 7.
Furthermore, the shapes of the molecular orbitals (MOs) for all compounds are illustrated in (Fig. 8). Generally, the
absorption spectra of the mentioned compounds are characterized by a large band at 300-400 nm, moderate absorption
bands (from 180 to 280 nm). We observe that the simulated spectra for ZnL exhibit prominent bands within the ranges
of 160-180 nm. Analysis of the molecular orbitals suggests that the electronic excitation at approximately 343 nm is
characterized by a combined character of ICT in ligand and small ICT in metal (see Fig.9). On the other hand, The TD-
DFT calculation on NiL, CuL and ZnL complexes shows that the wavelength of the largest oscillator strength (located
at 218, 220, 218 nm ( f(CuL) = 1.133, 0.854 and 1.408, respectively) ( H→ L+3/ H→L+3) are due to intra-ligand
charge transfer (ILCT) of type →* and n→* electron transition. The excited states S2 and S3 of Cu(II) complexes
are obtained at 549 and 498 nm respectively, it has a mixed metal-ligand charge transfer (MLCT) and ILCT character
(→* and n→*). TD-DFT calculation on Zinc complex reveals that the H →L+7 transition is associated with LMCT
from ligand to metal (at 204 nm, see Table 7). On the other hand, the analysis of the other excited states (S2, S5 and
S14) we can note that these transitions have a mixed ILCT (→* and n→*) character.

On the other hand, TD-DFT calculation on NiL complex (see Fig.10) shows that the βH-11→βL+4, β H-1→β L and
β H-5→β L transitions, located at 541 nm(f= 0.003), 377 nm (f= 0.023) and 287 nm(f= 0.003) are due to a mixed ICT
in metal and LMCT. The absorption obtained at 324 nm (f=0.184), it has LLCT character.

8
4.4 Nonlinear optical properties

Currently, considerable focus is placed on the investigation and advancement of novel nonlinear optical materials
owing to their potential applications in a various field, including photonics, optical fiber communication, optical
computing, optical switching, data storage, dynamic holography, photodynamic therapy, etc [27, 69-71]. In recent
years, the application of quantum chemical calculations employing the Density Functional Theory (DFT) methodology
has emerged as a crucial strategy for forecasting and elucidating nonlinear optical (NLO) responses in materials. [71,
72-76] In this study, we systematically examine the alterations in both linear and nonlinear optical properties of NiL,
CuL, and ZnL complexes within Static (=0) and dynamic ( 0.04282 a.u. regimes to investigate the influence of
transition metals on the NLO responses of the aforementioned complexes. The isotropic polarizability (((0;0) and
(;)) and its anisotropy polarizability (Δ(0; 0) and Δ(; )), first hyperpolarizability β0(0; 0,0), a.u), second
harmonic generation (βSHG (-2ω; ω,ω), a.u), DC Pockels effect (βEOPE (-ω; ω,0) a.u), hyper-Rayleigh scattering (βHRS ,
a.u) and depolarization ratio DR (static as well as dynamic) and second hyperpolarizability ((0;0,0,0)) are calculated
and provided in Table 8.
Referring to the results listed in Table 8, it is noticeable that the isotropic and anisotropy polarizability values at static
and dynamic regime for ZnL complex exhibit a slight decrease when compared to those of NiL and CuL. It can be
observed that the influence of laser intensity on the α and Δα values of these complexes is negligible. Furthermore, the
analysis reveals that the static first-hyperpolarizability (β0(0; 0,0) and βHRS) exhibits an ascending order from ZnL, CuL
to NiL, a pattern consistently observed in the static second-hyperpolarizability as well. From these observations, it can
be concluded that the magnitudes of both the first- and second-hyperpolarizabilities increase inversely with the atomic
number of the transition metal. For instance, the β0(0; 0,0) value of the NiL complex exceeds that of CuL and ZnL by
8% and 24%, respectively. Additionally, the γ(0;0,0,0) value for the NiL complex is greater than that of CuL and ZnL
by 42% and 90%, respectively.
As can be seen in Table 8, the first-hyperpolarizability value increases with increasing frequency of the incident light
i.e., β0(0; 0,0) is less than both βωSHG and βEOPE and similarly, β0HRS < βωHRS. On the other hand the CuL complex
display the larger βHRS, βSHG and βEOPE than the other complexes. For instance, the βEOPE of the NiL complex is
approximately 7% and 21% greater than that of the CuL and ZnL complexes, respectively. The βHRS value of the NiL is
about 43% and 32% greater than that of CuL and ZnL, respectively. Furthermore, quantum calculations reveal that the
magnitude of electrooptic Pockels effect (-; , 0) of these compounds decrease as the atomic number of the
transition metal increases.
The depolarization ratio (DR) is a pivotal parameter for evaluating the contribution of molecular first-
hyperpolarizability. Examination of both static and dynamic DR values, as detailed in Table 8, with respect to the
nonlinear optical (NLO) properties of NiL, CuL and ZnL complexes, categorizes them as dipolar molecules.
To delve deeper into the source of the first hyperpolarizability of the title complexes, a polarization scan of HRS
intensity I2ωΨV has been computed. The relationship between I2ωΨV and the polarization angle Ψ is depicted in Fig. 11.
Based on the data presented in Fig. 11, it is deducible that the depolarization ratio values exhibit insensitivity to both the
type of transition metal atom (Cu, Ni, and Zn) and the frequency of the incident light. It is noted that across both static
and dynamic regimes, the DR values diminish in the sequence: ZnL > NiL > CuL. From this figure, it is evident that
DR0.04282˃DR0.
On the other hand, the urea molecule serves as a benchmark compound in the examination of second-order nonlinear
optical responses of molecules and is frequently utilized for comparative analysis due to its prototypical nature. In
9
alignment with this, the first hyperpolarizability of urea was computed using the same theoretical framework. The
results from our study revealed that the studied complexes exhibited static and dynamic first-hyperpolarizability values
0.04282
surpassing those of the urea molecule (β0=40, βHRS=36, βSHG=46, βEOPE=45, 𝛽𝐻𝑅𝑆 = 39 a.u.).
From this investigation, it can be concluded that these complexes hold potential as novel candidates for the
development of materials suitable for second- and third-order nonlinear optical applications.
5 Conclusions

In this study, the N2O2 schiff base ligand tetradentate and its copper(II) complex were synthetized and characterized
using various spectral tools such as Uv-Vis, FT-IR, Raman and NMR, the results cinfirmed the propose compounds.
Suitable single crystals for X-ray analysis have been grown by slow evaporation an crystal structure of the complex was
obtained. All the major interatomic and intermolecular interactions have been discussed and explained. The evaluation
in vitro by Antibacterial activites with five bacteries, revealed a good activity for ligand L and did not exhibit any
inhibitory effect. The structural and reactivity parameters as well as the linear and nonlinear optical properties of
compounds under investigations differing by a transition metal (Ni, Cu and Zn) have been examined through DFT and
TD-DFT calculations. These calculations were conducted under both static and dynamic regimes using the ωB97XD/6-
311**G/SDD method. Quantum chemical calculations suggest that the first and second- hyperpolarizability (β0 , βHRS ,
βEOPE and γ(0; 0,0,0)) of the examined complexes decrease as the atomic number of the transition metal increases. On
the other hand, our research indicates that these complexes represent promising new materials for the development of
second- and third-order NLO applications. Moreover, the ML (M= Cu, Ni and Zn) complexes emerge as potent
candidates for second-order NLO materials, potentially advancing the progress in high-technology applications.

Acknowledgement

The principal author thanks the Chemistry Department, University of Mentouri Brothers, Constantine 1, Algeria and
Biotechnology Research Center-C.R.Bt-Constantine Algeria, for financing the study, for their collaboration in this
research, and all the authors who participe in this work. Also, the authors are very thankful to the “Université de Lyon ,
Université Claude Bernard Lyon 1, CNRS UMR 5280 , Institut des Sciences Analytiques, 69622 Villeurbanne Cedex,
France, for offering the computing facilities. HSE is grateful to the University of Neuchâtel for their support over the
years.

Author contribution All authors contributed to the study

Declarations

Ethics approval Not applicable.

Competing interests

The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.

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Figures

Figure 1

FT-IR spectra of ligand L and complex CuL

Figure 2

Resonance Raman spectra of ligand L and complex CuL

Figure 3
UV–Vis spectra of ligand L and complex CuL

Figure 4

The central bridge of the ligand, (-CH2--CH(CH3)-

Figure 5
A view of the crystal packing illustrating the voids occupied by the disordered solvent molecules

Figure 6

Optimized geometry for the studied complexes ML respectively ((M = Cu, Ni and Zn)

Figure 7

Atom-by-atom superimposition of the crystallographic geometry (red) over the optimized structure (blue)
for CuL complex
Figure 8

Calculated UV − vis absorption spectra of title compounds

Figure 9

The most prominent MOs involving electronic transitions for NiL, CuL and ZnL complexes
Figure 10

TD-DFT calculated absorption wavelength (α,nm) of virtual frontier MOs (HOMO)

and (LUMO) for the complexes

Figure 11

Evolution of the depolarization ratio (DR) in static and dynamic regime (red: dynamic regime, blue: static
regime)

Supplementary Files
This is a list of supplementary les associated with this preprint. Click to download.

Supplementarymaterial.docx
Tables.docx