Physico-Chemical Study of Mn(II), Co(II), Cu(II), Cr(III), and Pd(II) Complexes with Schiff-Base and Aminopyrimidyl Derivatives and Anti-Cancer, Antioxidant, Antimicrobial Applications

A new class of biologically active mineral complexes was synthesized by reacting the following metal salts: MnCl2·4H2O, CoCl2·6H2O, CuCl2·2H2O, CrCl3·6H2O, and PdCl2 respectively with 2-amino-4,6-dimethyl pyrimidine (ADMPY) and Schiff’s base resulting from the condensation reaction between benzaldehyde with p-phenylenediamine and 2-hydroxy-1-naphthaldehyde as ligands have been synthesized and characterized on the basis of their CHN, thermal analysis, XRD, SEM and magnetic measurements along with their FT-IR and UV-vis spectra. The scanning electron microscope SEM measurements and the calculations on the powder XRD data indicate the nano-sized nature of the prepared complexes (average size 32–88 nm). The spectral data confirmed the coordinated ligand (HL) via a nitrogen atom of an azomethine group (-C=N-) and phenolic -OH group and NH2-ADMPY ligand with the metal ions. An octahedral geometry for all complexes has been proposed based on magnetic and electronic spectral data except Pd(II) complex, which has a tetrahedral geometry. Molecular modeling was performed for Cu(II) complex using the density functional method DFT/B3LYP to study the structures and the frontier molecular orbitals (HOMO and LUMO). The antioxidant of the complexes was studied using the 2,2-diphenyl-1-picrylhydrazyl (DPPH)-free radical-scavenging assays. The metal complexes were tested in vitro for anticancer activities against two cancer lines A-549 and MRC-5 cells. Cu(II) and Pd(II) complexes showed the highest cytotoxicity effect, comparable to that of other cis-platinum-based drugs. The complexes showed significant activity against fungi and bacteria.


Introduction
Recently, the focus has been on mixed chelated mineral complexes due to their importance and biological activity against microbes, fungi, cancerous tumors, and others. Schiff bases are the most common coordination compounds. They were named Schiff bases in relation to their discovery by the German scientist Hugo Schiff, who discovered them in 1864. They were simply synthesized by condensing primary amines and carbonyl compounds [1]. The azomethine (anils, imines) group (-HC=N-) is a structural feature shared by these compounds. This active group carries a potential binding site for metal ions through the lone pair of electrons (unlinked) in a hybridized orbital SP 2 of the nitrogen atom. The (C=N) linkage is required for biological activity in azomethine derivatives; numerous azomethines have been reported to have strong antifungal, antibacterial, anticancer, and antimalarial properties. Numerous Schiff bases and their complexes have been investigated for their noteworthy and intriguing qualities, such as their photochromic qualities and capacity to bind to some toxic metals [2]. Here we find Schiff's base acting as a toothed flexible ligand and coordination is carried out through the nitrogen atom of the azomethine qualities and capacity to bind to some toxic metals [2]. Here we find Schiff's base a as a toothed flexible ligand and coordination is carried out through the nitrogen ato the azomethine group and the oxygen atom of the phenolic group. It is close to the methine group [3], so it was shown in studies that Schiff bases are excellent chel agents, and they also provide a great attraction factor due to the ease of preparation, s tural flexibility, and the special properties of the C=N group [4,5]. In addition, pyr derivatives are among the important categories in inorganic chemistry, where 2-am 4,6-dimethyl pyrimidine is one of its important derivatives, which plays an important role, as it participates in coordination. Pyrimidine is a member of the heterocyclic pound family and is a common substance found in living things. It holds a special pos in the field of heterocyclic and medicinal chemistry because of its beneficial biolo properties and therapeutic uses. Since the structural subunits of the pyrimidine pound are found in many naturally occurring products, including vitamins and ant ics, it is widely distributed in nature and is extremely important to human health. C quently, they pay close attention to the development of both biologically energetic pounds and antibiotics. Tri-substituted pyrimidine containing an electron-withdra group such as the amino group in pyrimidine shows more potent in vitro antimicr activity [6][7][8][9]. Thus, the synthesis and screening of Schiff base ligand, 2-((E)-((4-(((E) zylidene)amino)phenyl)imino)methyl)-naphthalene-1-ol with transition metal comp ability, anticancer activity, antioxidant properties, and antibacterial properties wou of substantial biological importance [10]. Previously, complexes of Cr(III), Mn(II), N Fe(III), and Zn(II) were reported to show anticancer, antioxidant, and antibacterial ac [10]. Therefore, we speculate that complexes of Mn(II), Co(II), Cu(II), Cr(III), and P with 2-amino-4,6-dimethyl pyrimidine (ADMPY) and Schiff's base will show more cancer, antibacterial, and antioxidant activity. These findings prompted us to start a ject on metal-ADMPY and Schiff's base complexes, involving an investigation of nano-sized, anticancer, antibacterial, and antioxidant properties. The main objecti this research is to prepare and study the physico-chemical composition of the new n sized complexes of manganese(II), cobalt(II), copper(II), chromium(III), and palladium which are studied in solution and in the solid state. The stability constants are evalu and structure of the studied complexes is elucidated using elemental analyses, FT-IR vis spectra, magnetic moment, molar conductance, and thermal analyses measurem

Results and Discussion
The reactions of manganese(II), cobalt(II), copper(II), chromium(III), and palladium(II) with HL and (ADMPY) ligands proceed readily to form the corresponding mixed ligand complexes. The metal mixed-bonding complexes were respectively prepared at a ratio of M:L1:L2 (1:1:1). The complexes are air-stable, insoluble in common organic solvents Molecules 2023, 28, 2555 3 of 21 but soluble in dimethylformamide (DMF) and dimethylsulphoxide (DMSO). The molar conductivities of the complexes in DMSO at 25 • C are in the 11.4-28.2 Ω −1 cm 2 mol −1 range indicating the non-electrolytic nature of the compounds [11][12][13]. The following figure ( Figure 2) illustrates these suggested summary formulas.

Fourier Transform Infrared Spectra
The IR spectra provide important information about the nature of the functional group attached to the metal. The IR spectrum of the free ligands is compared to the spectra of the complexes to study the bonding mode of Schiff base and (ADMPY) ligands to metal complexes. Table 1 shows the main IR bands and their assignments. FTIR spectrum of ligand (HL) did not show the stretching frequency of phenolic (O-H) because of its involvement in hydrogen bonding (intra-ligand hydrogen bond) with lone electron pair of an azomethine nitrogen atom (O-H . . . . . . N) [14]. The υ(O-H) vibrations of complexes 1, 2, 3, 4 and 5 were observed as strong bands at 3410, 3345, 3438, 3326, and 3354 cm −1 respectively. Strong bands appear at 1618, 1604 cm −1 belonging to the two azomethine groups υ(C=N) [15]; it also shows a medium band of the υ(C=C) at 1540 cm −1 [16]; the stretching frequency of the phenolic υ(C-O) bond has been recorded as 1310 cm −1 . The spectrum of ligand (ADMPY) observed the medium intensity absorption bands 3396 cm −1 and 3310 cm −1 are due to asymmetric and symmetric vibrations of υ(NH 2 ) stretching frequency, respectively, while the bending band-specific scissors at 1633 cm −1 appears [17], C-N. It is found in two places; the base ring and the primary amine group. Comparisons were made by contrasting the compound's spectrum with published literature on similar systems. It was found that the stretching frequency of the phenolic υ(C-O) bond has been shifted in spectra of prepared complexes of the υ(C-O) stretching band, which provides evidence that the phenolic-OH group is involved in chelation. This chelation is further reinforced also by the appearance of new peaks in complexes due to δ(OH) rocking [18], its blue-shift indicates the sharing of phenolic oxygen atom in coordination with metal ions after losing its proton. The azomethine group υ(C=N) in all complexes undergoes a shift, necessitating its coordination with the metal center. Because the NH 2 group of the ADMPY ligand will be overlapping with those of the water molecules, the presence of water coordination in the complexes' spectra makes it challenging to conclude them. Clarifying how chelation affects the in-plane bending, or δ(NH 2 ) vibration, adds to the evidence that the NH 2 group is involved. This band's shift from 1633 cm −1 in the free ADMPY ligand to 1667-1698 cm −1 in the complexes shows that the NH 2 group was involved in complex formation [19]. The υ(OH) in the lattice H 2 O in complexes (2) and (4) may be ascribed to a broad diffused band with medium intensity situated at 3547 and 3548 cm −1 respectively [20,21]. The coordinated H 2 O υ(OH) stretching vibration for the complexes (1) through (5) appears at a wavelength of 3302-3330 cm −1 ranges in each case. A band at 732-747 cm −1 in the IR spectra of the complexes 1-5 appears as (H 2 O), this suggests that coordinated water is present [22]. New bands are found in the spectra of the complexes in the regions 640-612 cm −1 which are assigned to υ(M-O). The bands at 566-544 cm −1 have been assigned to υ (M-N) of the amino mode [23]. The υ(M-Cl) bands appeared at 442-419 cm −1 [24].

Magnetic Moments
At room temperature, the magnetic moment (µeff) values for the complexes (1-4) are given in Table 2 [25,26]. The magnetic moment of the Cu(II) complex was 1.72 BM, which is consistent with an octahedral shape and one unpaired electron [27]. Indicating the presence of three unpaired electrons in its outer valence shell and creating an octahedral geometry around the Cr(III) ion, the Cr(III) complex displayed a magnetic moment of 3.70 BM [28]. The diamagnetic behavior of the Pd(II) complex suggests a square-planar geometry [29,30].

Electronic Spectra
Electronic spectra of metal complexes and free ligands (HL), (ADMPY) use DMSO (10 −3 M) as solvent ( Table 2). The ligand UV-Vis spectrum (HL) peaks at 259 nm are assigned to (π→π * ) [10]. The ligand (ADMPY) showed absorbance bands at 314 assigned to (n→π * ) [6]. As for the electronic spectra of complexes for Mn(II), Co(II), Cu(II), Cr (III), and Pd(II), it has distinct bands in the visible region of spectra attributed to d-d transitions ranges at 415-455 nm. As for the bands corresponding to the π→π * and n→π * , transitions appeared in the ranges of 252-308 nm and 300-355 nm, respectively, which indicates a bonding between the ligand and the metal elements. We may suggest the following chemical formulae for the produced five metal mixed ligand complexes based on the previously collected data elemental analyses, infrared and electronic spectra, magnetic moment measurements, and molar conductance measurements ( Figure 3). (a)

Theoretical Study
We carried out the DFT optimization through PBE1PBE functional using 6-31G (d)/Lanl2dz basis sets. The copper center is five coordinated ( Figure 4) and bonded to the first ligand with Cu-N i(2.02 Å) and Cu-OH (2.23 Å). It is also bonded to 2 Cl (2.32 Å and 2.32 Å). For the second ligand, it is bonded to NH2 with a distance Cu-NH2 = 2.13 Å. The electron density is distributed on the first ligand for the HOMO ( Figure 5) but it is mainly distributed on the metal for the LUMO.

Theoretical Study
We carried out the DFT optimization through PBE1PBE functional using 6-31G (d)/Lanl2dz basis sets. The copper center is five coordinated ( Figure 4) and bonded to the first ligand with Cu-Ni (2.02 Å) and Cu-OH (2.23 Å). It is also bonded to 2 Cl (2.32 Å and 2.32 Å). For the second ligand, it is bonded to NH 2 with a distance Cu-NH 2 = 2.13 Å. The electron density is distributed on the first ligand for the HOMO ( Figure 5) but it is mainly distributed on the metal for the LUMO.

Theoretical Study
We carried out the DFT optimization through PBE1PBE functional using 6-31G (d)/Lanl2dz basis sets. The copper center is five coordinated ( Figure 4) and bonded to the first ligand with Cu-N i(2.02 Å) and Cu-OH (2.23 Å). It is also bonded to 2 Cl (2.32 Å and 2.32 Å). For the second ligand, it is bonded to NH2 with a distance Cu-NH2 = 2.13 Å. The electron density is distributed on the first ligand for the HOMO ( Figure 5) but it is mainly distributed on the metal for the LUMO.

Thermal Analysis
The DTA and TGA curves in the temperature range 20-550 °C for the complexes appear at a heating rate of 10 °C/min; they showed an agreement in weight loss between their results obtained from the thermal decomposition and the calculated values, which supports the results of elemental analysis and confirms the suggested formulae. TG analysis results of mixed ligand complexes are summarized in Table 3, it was possible to determine the following characteristic thermal parameters for each reaction step: Initial point temperature of decomposition (Ti): the point at which TG (Tm) curve starts deviating from its base line. Final point temperature of decomposition (Tf): the point at which TG curve returns to its base line. Table 3. Thermal decomposition data of complexes.

Compound
Step

Thermal Analysis
The DTA and TGA curves in the temperature range 20-550 • C for the complexes appear at a heating rate of 10 • C/min; they showed an agreement in weight loss between their results obtained from the thermal decomposition and the calculated values, which supports the results of elemental analysis and confirms the suggested formulae. TG analysis results of mixed ligand complexes are summarized in Table 3, it was possible to determine the following characteristic thermal parameters for each reaction step: Initial point temperature of decomposition (Ti): the point at which TG (Tm) curve starts deviating from its base line. Final point temperature of decomposition (Tf): the point at which TG curve returns to its base line. Table 3. Thermal decomposition data of complexes.

Compound
Step  One water molecule's loss (calculated at 2.69%, found at 2.51%) and the observed mass loss of this initial stage are closely correlated. Two chlorine atoms (calculated at 10.60%, measured at 10.34%) are responsible for the observed mass reduction in the second step.
The final step (calculated at 70.83%, discovered at 69.56%) represents the breakdown of the remaining organic ligands. A large exothermic peak at 360 • C on the DTA curve designates this stage. The ultimate product at 450 • C is consistent with the formation of palladium oxide as a residual part was found to be (17.98%), compared to the (18.30%) calculated ( Figure 6).

X-Ray Powder Diffraction (XRD)
This XRD study is also one of the pieces of evidence about the formation of metalligand complexes. The manganese(II), cobalt(II), copper(II), chromium(III) and palla-

X-ray Powder Diffraction (XRD)
This XRD study is also one of the pieces of evidence about the formation of metalligand complexes. The manganese(II), cobalt(II), copper(II), chromium(III) and palladium(II) complexes were chosen for X-ray powder diffraction studies. The samples are irradiated with a beam of monochromatic X-rays over a variable incident angle range. The X-rays were detected using a fast-counting detector based on silicon strip technology (Bruker LynxEye detector). Interaction with atoms in the sample results in diffracted X-rays when the Bragg equation is satisfied. The X-rays were detected using a fast-counting detector based on silicon strip technology (Bruker LynxEye detector). XRD patterns are shown in Figure 7. All the samples are characterized at room temperature by X-ray diffraction using Cu Kα radiation. The diffraction pattern of complexes is recorded between 2θ ranging from 10 • to 80 • . The particle size of the samples is estimated using Scherrer's formula. According to Scherrer's equation, the particle size is given by t = 0.9 λ/Bcosθ, where t is the crystal thickness (in nm), B is half width (in radians), θ is the Bragg angle, and λ is the wavelength. The particle size corresponding to each diffraction maxima is determined from the measurement of the half-width of the diffraction peak. The value of the Lattice parameter and the particle size are shown in Table 4 for all five complexes. The Mn(II) complex is monoclinic, that of the Pd(II) and Co(II) complexes are tetragonal, and those of the Cu(II) and Cr(III) complexes belong to the triclinic crystal system. All metal complexes exhibit sharp peaks. The particle size was found to be within the range of 32-88 nm for all the complexes.

Morphological and Structural Properties of Synthesized Metal-Ligand Complexes
Scanning electron microscopy (SEM) was used to assess the mixed ligand metal complexes' morphological and structural characteristics, as morphology changes when the metal ions are changed. The SEM image of Mn(II) complex revealed small particles of irregular shape. The Co(II) complex shows road-shaped particles, whereas Cr(III) complex exhibits granular texture. Finally, The Pd(II) complex shows a figure of branched nanowires. The SEM micrographs are shown in Figure 8. Thus, these SEM results confirmed the nanostructured behavior of the synthesized metal complexes.

Morphological and Structural Properties of Synthesized Metal-Ligand Complexes
Scanning electron microscopy (SEM) was used to assess the mixed ligand metal complexes' morphological and structural characteristics, as morphology changes when the metal ions are changed. The SEM image of Mn(II) complex revealed small particles of irregular shape. The Co(II) complex shows road-shaped particles, whereas Cr(III) complex exhibits granular texture. Finally, The Pd(II) complex shows a figure of branched nanowires. The SEM micrographs are shown in Figure 8. Thus, these SEM results confirmed the nano-structured behavior of the synthesized metal complexes.

In Vitro Anticancer Activities
Cancer is a type of malignant disease in which a group of cells appears to grow in an irregular pattern. The only way to treat this is through surgical intervention or chemotherapy, both of which have negative side effects. Although platinum-based complexes such as cis-platin have been used to treat cancer, it is not effective, so in vitro tests for complexes of manganese, cobalt, copper, chromium, and palladium were conducted against two cancer lines, respectively. A-549 and MRC-5 cells were used as test subjects for the cytotoxic

Biological Activity 2.8.1. In Vitro Anticancer Activities
Cancer is a type of malignant disease in which a group of cells appears to grow in an irregular pattern. The only way to treat this is through surgical intervention or chemotherapy, both of which have negative side effects. Although platinum-based complexes such as cis-platin have been used to treat cancer, it is not effective, so in vitro tests for complexes of manganese, cobalt, copper, chromium, and palladium were conducted against two cancer lines, respectively. A-549 and MRC-5 cells were used as test subjects for the cytotoxic activity of Schiff base and aminopyrimidyl complexes in the concentration range of 0-500 (g/mL). Results are provided in Figure 9, which shows the IC50 and CC50 values for each compound (Table 5)      (1-6) Cells were exposed to different concentrations of the compounds for 72 h. Cell viability was determined by a colorimetric method.

Antimicrobial Activity Antifungal Screening
The data shown in Table 6 showed excellent activity against fungal strains, specifically against the fungal strain Cryptococcus nanoforms. We note that the growth inhibition zone ranged between 9 and 40. We also note that many mineral complexes showed higher activity than the control sample compared to the lower antifungal activity of the free ligand or the previous complexes [10]. We found that palladium(II) and copper(II) complexes are the most active against fungi which showed impressive activity, while the manganese(II) complex is the least effective (Figures 11-13). The complexes were arranged according to their activity against fungal strains as follows: Pd(II) > Cu(II) > Co(II) > Cr(III) > Mn(II).

Antibacterial Screening
The data in Table 7 showed activity against bacterial strains, where the palladium(II) and copper(II) complexes showed the highest zone of inhibition compared to the rest of the complexes, and manganese(II) complexes were found to be the least effective ( Figure  14). The complexes were arranged in the following order based on their activity against bacterial strains: Pd(II) > Cu(II) > Co(II) > Cr(III) > Mn(II) Table 7. Biological activities of the complexes against Gram-positive bacteria.

Antibacterial Screening
The data in Table 7 showed activity against bacterial strains, where the palladium(II) and copper(II) complexes showed the highest zone of inhibition compared to the rest of the complexes, and manganese(II) complexes were found to be the least effective ( Figure 14).
The complexes were arranged in the following order based on their activity against bacterial strains: Pd(II) > Cu(II) > Co(II) > Cr(III) > Mn(II)  Complexes are typically more effective and active against Gram-positive bacteria than Gram-negative bacteria compared to the lower antibacterial activity of the free ligand or the previous complexes [10]. This could be explained by the fact that Gram-positive bacteria have dense cell walls with many layers of teichoic acids and peptidoglycan. Gram-negative bacteria, on the other hand, have a relatively thin cell wall made up of a few peptidoglycan layers that are encircled by a second lipid membrane that contains lipoproteins and lipopolysaccharides. The variance in the structure of the cell wall led to differences in antibacterial activity. Figures 15 and 16 demonstrate that the tested complexes are effective against Gram-positive and negative bacteria. Complexes are typically more effective and active against Gram-positive bacteria than Gram-negative bacteria compared to the lower antibacterial activity of the free ligand or the previous complexes [10]. This could be explained by the fact that Gram-positive bacteria have dense cell walls with many layers of teichoic acids and peptidoglycan. Gram-negative bacteria, on the other hand, have a relatively thin cell wall made up of a few peptidoglycan layers that are encircled by a second lipid membrane that contains lipoproteins and lipopolysaccharides. The variance in the structure of the cell wall led to differences in antibacterial activity. Figures 15 and 16 demonstrate that the tested complexes are effective against Gram-positive and negative bacteria.
or the previous complexes [10]. This could be explained by the fact that Gram-positive bacteria have dense cell walls with many layers of teichoic acids and peptidoglycan. Gram-negative bacteria, on the other hand, have a relatively thin cell wall made up of a few peptidoglycan layers that are encircled by a second lipid membrane that contains lipoproteins and lipopolysaccharides. The variance in the structure of the cell wall led to differences in antibacterial activity. Figures 15 and 16 demonstrate that the tested complexes are effective against Gram-positive and negative bacteria.

Antioxidant Assays
Oxidation in living organisms caused by free radicals are usually undesirable processes damaging such important biomolecules as DNA, proteins, and lipids [31].
The application of antioxidants is one of the most straightforward means to protect these biomolecules from oxidative stress. Many assays are available for the determination of antioxidant potential in vitro. These assays are based on the reduction of stable radicals (DPPH). DPPH test is one of the most commonly performed antioxidant assays with natural and (semi)synthetic biologically active compounds. Although it has no direct physiological relevance, this assay allows quick comparison of the free radical scavenging potential of new derivatives as this activity has been published for many compounds [32]. We have therefore tested our mixed ligand complexes of Schiff bases and aminopyrimidyl derivatives for DPPH scavenging and compared their activity with the activity of the parent compounds, that is, Cu(II) and Pd(II) complexes showing high activity, Co(II) and Cr(III) complexes showing moderate activity, and all of them showing less activity when compared to the standard (ascorbic acid). Under these experimental conditions, the Mn(II) complexes demonstrated weak antioxidant activity. The IC50 values for all the collectors were determined and compared with the standard as listed in the Table 8 and Figure 17.

Antioxidant Assays
Oxidation in living organisms caused by free radicals are usually undesirable processes damaging such important biomolecules as DNA, proteins, and lipids [31].
The application of antioxidants is one of the most straightforward means to protect these biomolecules from oxidative stress. Many assays are available for the determination of antioxidant potential in vitro. These assays are based on the reduction of stable radicals (DPPH). DPPH test is one of the most commonly performed antioxidant assays with natural and (semi)synthetic biologically active compounds. Although it has no direct physiological relevance, this assay allows quick comparison of the free radical scavenging potential of new derivatives as this activity has been published for many compounds [32]. We have therefore tested our mixed ligand complexes of Schiff bases and aminopyrimidyl derivatives for DPPH scavenging and compared their activity with the activity of the parent compounds, that is, Cu(II) and Pd(II) complexes showing high activity, Co(II) and Cr(III) complexes showing moderate activity, and all of them showing less activity when compared to the standard (ascorbic acid). Under these experimental conditions, the Mn(II) complexes demonstrated weak antioxidant activity. The IC50 values for all the collectors were determined and compared with the standard as listed in the Table 8 and Figure 17.

Physical Measurements for Complexes
The FTIR spectra of the ligand and its metal complexes in the solid state were measured using Agilent technologies/Gladi-ATR, USA) Cary 600 Series FTIR Spectrometer in the wave range 400-4000 cm −1 . The carbon, hydrogen, and nitrogen contents were determined for the prepared ligand and its metallic complexes using a Eurovector CHN (EA3000, Italy) analyzer. Magnetic moments were measured using a Sherwood Scientific magnetic susceptibility balance (MSB-Auto) (UK). Electron-visible and UV-visible absorption spectra of (DMSO, 1 × 10 −3 M) solutions were also recorded on a Shimadzu 1650-Spec UV-Vis spectrometer (Shimadzu, Duisburg, Germany). Thermal analysis of the compounds was carried out in dynamic air on a Shimadzu (DTG 60-H) thermal analyzer at a heating rate of 10 °C/min, the temperature range was 20-600 °C. XRD Model (PW 1710) control unit Philips with a Cu Kα (l = 1.54180 Å) anode at 40 K.V 30 M. A scanning electron microscopy (SEM) was used to examine the morphology of the complexes (JEOL JSM-5400-LV Field Emission SEM, Tokyo, Japan).

Physical Measurements for Complexes
The FTIR spectra of the ligand and its metal complexes in the solid state were measured using Agilent technologies/Gladi-ATR, USA) Cary 600 Series FTIR Spectrometer in the wave range 400-4000 cm −1 . The carbon, hydrogen, and nitrogen contents were determined for the prepared ligand and its metallic complexes using a Eurovector CHN (EA3000, Italy) analyzer. Magnetic moments were measured using a Sherwood Scientific magnetic susceptibility balance (MSB-Auto) (UK). Electron-visible and UV-visible absorption spectra of (DMSO, 1 × 10 −3 M) solutions were also recorded on a Shimadzu 1650-Spec UV-Vis spectrometer (Shimadzu, Duisburg, Germany). Thermal analysis of the compounds was carried out in dynamic air on a Shimadzu (DTG 60-H) thermal analyzer at a heating rate of 10 • C/min, the temperature range was 20-600 • C. XRD Model (PW 1710) control unit Philips with a Cu Kα (l = 1.54180 Å) anode at 40 K.V 30 M. A scanning electron microscopy (SEM) was used to examine the morphology of the complexes (JEOL JSM-5400-LV Field Emission SEM, Tokyo, Japan).

Computational Studies
The density functional theory (DFT) was performed by using Gaussian09 program. The optimization of the diverse Cu(II) complex was done by DFT through the functional B3LYP and Lanl2dz/6-31G(d) basis sets. LANL2DZ basis set was limited for the treatment copper(II) atom and 6-31G(d) basis set for all other atoms. To confirm the stability of the structures, we calculated the vibrational frequencies at the same level of theory.

Antioxidant Activity
The antioxidant activity of the extract was determined at the Regional Center for Mycology and Biotechnology (RCMB) at Al-Azhar University by the DPPH free radical scavenging assay in triplicate, and average values were considered.

(DPPH) Radical Scavenging Assay
Freshly prepared (0.004% w/v) methanol solution of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical was prepared and stored at 10 • C in the dark. A methanol solution of the test compound was prepared. About 40 uL aliquot of the methanol solution was added to 3 mL of DPPH solution. Absorbance measurements were recorded immediately with a UV-visible spectrophotometer (Milton Roy, Spectronic 1201). The decrease in absorbance at 515 nm was determined continuously, with data being recorded at 1 min intervals until the absorbance stabilized (16 min). The absorbance of the DPPH radical without antioxidant (control) and the reference compound ascorbic acid were also measured. All the determinations were performed in three replicates and averaged. The percentage inhibition (PI) of the DPPH radical was calculated according to the formula: where AC = absorbance of the control at t = 0 min and AT = absorbance of the sample + DPPH at t = 16 min. A 50% inhibitory concentration (IC50) or the concentration required for 50% DPPH radical scavenging activity was calculated.