View of Synthesis and Spectral Studies of Some New Complexes Containing Azo Ligand with Anticancer, Antibacterial and Dyeing Performance.

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Annals of R.S.C.B., ISSN:1583-6258, Vol. 25, Issue 4, 2021, Pages. 7968 - 8006 Received 05 March 2021; Accepted 01 April 2021.

7968 http://annalsofrscb.ro

Synthesis and Spectral Studies of Some New Complexes Containing Azo Ligand with Anticancer, Antibacterial and Dyeing Performance.

Rehab Abd Al-

[email protected]@yahoo.comaalyakhiderDepartment of chemistry ,College of science, university of Baghdad

Abstract

The new designed N,N-bidentateazo ligand 8-[1- (4- sulfonic acid naphtyl) azo]

theobromine (SNT), has been synthesized by diazotization and couple for naphthanoic acid and theobromine. The ligand (SNT) was reacted with [Ni(II), pd(II), pt(IV) and Cu(II) to give novel complexes. Both ligand and it's metal complexes were characterized by usual spectroscopic techniques, thermal analysis, magnetic measurement and molar conductance data. The stoichiometric of the complexes were found by mole ratio method and it was (I:2) (M:L) the Ni(II) and pt(IV) complexes found to have octahedral structure while the Cu(II) and pd(II) complexes have distorted octahedral and square planar respectively. The dyeing performance, antibacterial and anticancer activities were investigated for SNT ligand it's complexes.

Keywords: -metal complexes, Theobromine, spectroscopic, anticancer, dying per- Formance

Introduction

The majority of synthesized organic compounds have been influenced by azocompounds because they are particularly fruitful in drugs[1], dyes and cosmetics[2].

These molecules are more soluble than natural dyes at a wide pH ranges and are also thermally stable[3-5].Because of their biological properties, such as antiinflammatory[6]

anticancer[7], antibacterial[8] and antifungal[9], azo compounds have been more imperative nowadays. In the world of medicine and pharmacology[10], a terribly significant role is often found to play. Due to their flexible usage in various industrial applications such as coloring fibers[11], they have gained a lot of consideration.

Theobromine, formerly referred to as xantheose by the name 3,7-dihydro-3,7- dimethyl-1H-purine-2,6-dione or 3,7-dihydro-3,7-dimethyl-1H-purine-2,6-dione (3,7- Dimethylxanthine) from theobromacacoa; theo = god, and broma = food; hence, food of the gods [15-16]. Theobromine is the cacao bean's primary alkaloid, which comprises 1.5 to 3 percent of the base and is thus contained in chocolate[17,18]. As a methylated xanthine, theobromine is a potent inhibitor of cyclic adenosine monophosphate phosphodiesterase (CAMP), inhibiting the conversion of the active enzyme phosphodiesterase (cAMP) into an inactive state. In separate metabolic processes, (cAMP) is a second messenger. Theobromine can act as a starting material for the preparation of pentoxifylline, a derivative of methylxanthine. Pentoxifylline increases blood supply and is used for the prevention of vascular dementia and intermittent claudication [19-20].

The present work aims to synthesis and characterize the geometrical structures biological activity and cytotoxicity assay of novel N,N- bidentateligand 8-[1-(4-sulfonic acid naphthyl) azo] theobromine (SNT) and its metal complexes with Ni (II) , Cu (II) , Pd (II) , Pt (IV).

1-MATERAILS AND METHODS Material and Physical measurements

All the material and solvents were utilized of highest purity. Elemental analyses and metal content for the ligand and its complexes were measured by using (C.H.N.S) was obtained on (Eure EA 3000 Elemental analyzer) and the percentage of metal in complexes

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was done by using a ―GBC 933 Plus ―Flam Atomic Absorption Spectrophotometer. FT-IR spectrophotometry Fourier Transform Infra-Red spectra were recorded by SHIMADZU 8400s spectrophotometer in the rang (250- 4000) cm-1 with CsI. UV-Vis Spectra for all the studied compounds were recorded on the (SHIMADZU 1800 – UV-Visspectrophotometer) using DMSO in the range of (250-1100) nm. The ¹H-NMR spectra were measured on a BRUKER AV 400 Avance -III (400 MHz and 100MHz) instrument with tetramethylsilane as the internal standard. Thermal analysis (TGA and DSC) of the metal content of the synthesized ligands and complexes were determined by utilizing (SDT Q600 V20.9 Build).

The melting points for all the compounds were performed by Gallenkamp melting point apparatus. The molar conductivity for metal ion complexes were studied in DMSO (10^-3 M), which were determined to Hunts Capacitors Trade Mark British made. The chloride contents of the studied complexes were carried out by using Mohr method. The magnetic susceptibility of the studied complexes was performed at room temperature by Auto Magnetic Susceptibility Balance Model Sherwood Scientific. The SEM was performed by (quanta FEG 450).

2-Synthesis of (SNT) ligand

The ligand 8-[1-(4-sulfonic acid naphthyl) azo] thebromine (SNT) Was synthesized according to the method reported in the literature[21] with some modification as was shown in scheme below:-

The azo- theobromine ligand was synthesized, via preparation of diazonium salt (0.01 mole, 2.232 gm) of naphthionic acid dissolved in an ice acidic media (10 ml distilled water. and 10 ml conc. HCl). The 10 ml of 10% sodium nitrite was added carefully and dropwise at (0^oC). Subsequently the diazonium salt was stirred for (30 min) to complete the diazotation.

The coupling component of theobromine (0.01 mole, 1.801 gm) was dissolved in cold 5 % ethanolic basic solution (KOH). After the diazotation was complete the diazonium salt solution was added drop by drop to alkloide solution of theobromine with stirring at (0^oC). The pink precipitate was appeared and the pH value was adjusted to a neutral value (pH = 5-6), then left synthesis of complexes overnight for complete precipitation. After that filtered and washed with (1:1) (ethanol:H₂O) to remove the trace of starting material then dried.

Synthesis of metal complexes

[ Ni(II) , pd(II), pt (II) and Cu(II) ] complexes were synthesized in a mole ratio (1:2) (M:L) by dissolving of metal chloride (0:237,0.383,0.486 and 0.134) gm. (0.00lM) respectively. An ethanolic solution of the ligand (SNT) [0.828 gm., 0.002M]

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was added gradually while stirring. After that reflexed for (3) hours and the reaction was followed with TLC.

The colored precipitate was filtered off and washed several times with (1:1) (distilled water: ethanol). Finally left dry and collect. Table (1) was appeared the some physicochemical properties and elemental analysis for the ligand ( SNT) and it's complexes.

Table(1): physicochemical properties and elemental analysis

Compounds (M.wt) (gm/mol)

Yield (m.p)

℃

Color (𝛌𝐌𝐚𝐱)

nm

% elementcal analysis experimental (theoretical)

𝚲𝒎 𝒐𝒉𝒎^−𝟏𝒄𝒎^−𝟐

mol^-1

C H N S M Cl

SNT(C17H14N6O5S)

(414.404) 77.75

(324-326)

Pale Pink (512)

49.90 (49.22)

3.61 (3.37)

21.79 (20.27)

4.54 (3.86)

--- ---

---

[Ni( C17H14N6O5S) 2Cl2] (958.498)

76.32 (298-300)

magneta (520)

43.53 (42.56)

2.55 (2.92)

17.92 (17.52)

6.38 (6.67)

7.19 (6.1 2)

6.49 (7.40)

2

[Cu( C17H14N6O5S )2Cl2] (963.348)

83.26 (280-282)

Green brown

(616)

44.06 (43.59)

4.07 (3.11)

12.63 (17.43)

4.37 6.64

6.06 (6.5 9)

7.36 (7.37)

4

[Pd(C17H14N6O5S )2] Cl2 .H2O

(1024.228) 87.11

(300-302)

Dark purple

(556)

39.65 (39.83)

2.94 (2.73)

16.70 (16.40)

6.55 (6.24)

11.0 2 (10.

39)

6.51 (6.93)

77

[Pt( C17H14N6O5S

)2 Cl2]Cl2 .H2O 86.94 (310-312)

Dark green

34.85 3.41 14.25 5.80 16.7 3

11.43 76

3-Result and Discussion

Generally, all complexes were synthesized by reacting the azo ligand (SNT) to the selected metal salts using (1:2) ( M:L) mole ratio, while the ligand was synthesized via diazotization naphthenic acid in acidic media and then coupling with alkaloid theobromine as nucleophile All synthesized compounds were colored, which is a general characteristic of azo compound due to trans mutation in the delocalization of electrons[22]. The data was gained from atomic absorption to determine the metal percentage &, chloride percentage by Mohr method and elemental analysis were in satisfactory convention with general formulae was specified for the ligand (SNT) and it's metal complexes. The molar conductivities data in ethanol for [ Ni(II) and Cu(II)] complexes are (2and4) 𝑜ℎ𝑚⁻¹𝑐𝑚².mol respectively which was indicated non electrolytic nature but regard on[ pd(II) and pt(IV) ] had (77and 76) 𝑜ℎ𝑚⁻¹𝑐𝑚²mol^-1 which were possessed (I:2) electrolytic nature as was abulated in Table 1. Also the proposed structure support by spectroscopicmeasurement (FT- IR, HNMR and UV- Vis) and thermal analysis. The ligand (SNT) and their solid complexes are thermally stable and unaffected by moisture and atmospheric gases

4-Mole ratio

The mole ratio for the ligand (SNT) and its [Ni(II), Pd (II), Pt (IV) and Cu (II)]

complexes were explored applying The mole ratio method [23], which it is the most familiar technique utilized toidentifythenatureofthecomplexesformedinsolutionwantingisolation. This

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technique was measured absorbance versus molar ratio of the (M:L) whentheamountoftheligandisvaried(0.25ml)astheamountofthemetal ion is held constant, then the complex was formed and there is no retable dissociation, such a plot affords a sharp break. At this point indicates the composition ofcomplexes.

Figure (1) was shown the relationship between the absorbance and (M:L) ratio

while the date was listed in Table (2) .The

datareveal(1:2)(M:L)forallsynthesizedcomplexes

Table (2): Absorbance versus mole ratio for SNT-Metal ion in solution

M:L Absorbance

Ni(SNT) Cu(SNT) Pd(SNT) Pt(SNT)

1:0.25 0.00 0.630 0.55 0.25

1:0.50 0.18 0.841 0.73 0.40

1:0.75 0.52 0.930 0.88 0.71

1:1.00 0.75 1.110 1.11 0.89

1:1.25 0.93 1.270 1.30 1.19

1:1.50 1.11 1.360 1.45 1.28

1:1.75 1.25 1.450 1.55 1.49

1:2.00 1.27 1.510 1.61 1.51

1:2.25 1.30 1.530 1.62 1.56

1:2.50 1.33 1.520 1.65 1.58

1:2.75 1.39 1.540 1.66 1.61

1:3.00 1.40 1.501 1.64 1.60

1:3.25 1.44 1.550 1.65 1.61

1:3.50 1.44 1.540 1.62 1.59

1:3.75 1.45 1.560 1.63 1.58

1:4.00 1.40 1.510 1.67 1.59

Figure (1): Mole Ratio for the ligand (SNT) and its complexes.

Mole ratio C_m/C (SNT)

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5-stability constant and Gibbis free energy

Itispossibletofindthestabilityconstantspectrophotometrically.For the Complexes with mole ratio (1:2) (M:L) we use the following equations [24].

𝐾 =(1 − 𝑎)

4𝛼³𝑐² 𝛼 =(𝐴𝑚 − 𝐴𝑠) 𝐴𝑚

While: C=molar concentration of the complexes in molar , c = 10⁻³𝑀 α = degree of dissociation

A_S= the absorption of solution containing (1:1) stoichiometric (M:L) A_m =the absorption of solution containing (1:2) stoichiometric (M:L)

The above equation can be applied to all synthesized complexesTable (3) collect all the results were obtained .The stability of the complexes as below.

The thermodynamic parameters behavior of ∆G(Gibbs free energy) were also computed from the equation:

∆G = - RT ln K Where:

R=gas constant = 8.31 J. mole^-1. K T = absolute temperature (Kelvin)

And we conclude from the results that the retation to synthesis the complexes are spontanous

Table (3): The stability constant (K) and Gibbs free energy (∆G) for synthesized complexes

Complex As Am K Log K ∆G

[Ni( SNT )2Cl2] 0.75 1.27 22.36*10⁵ 14.6 -36449.07 [Cu(SNT )2Cl2] 1.110 1.510 10525.71 16.16 -39993.22 [Pd(SNT )2] Cl2 .H2O 1.11 1.61 5790339.36 15.57 -1.432 [Pt(SNT )2Cl2]Cl2 .H2O 0.84 1.51 2140131.45 14.57 -36053.21 6-FT-IR ‎

The main target of studying FT-IR spectra is to find out the nature of bonded between the ligand and the metal ion, as well as which of the active groups are affected by chelation when comparing the spectra of metal ions with the spectrum of the free ligand.

Which represented by obtaining bands splitting, shifts in band position, intensity change, disappearance of bands and appearance of new bands [25]. The assignments of bonding sites of the ligand (SNT) and its selected metal ions complexes were readily assigned depeneding on comparison with literature data [Table (4 )] in cesium iodide

In the FT-IR spectrum of (SNT) (Figure2)

Thebandsdetectedat(3458,1695,1670,1550,1485,1456,1432,1397 ,1226and1145)cm^-

1wereascribedtoʋ (NH),ʋ(C=N),ʋ(C=C),ʋ(N=N),ʋ (C-N=N- C)andʋ (SO₃H)respectively,[ s t r u c t u r e ( 1 ) ] whilethe FT-IR spectra for [Ni(II), Pd(II), Pt(IV) and Cu(II)] complexes Figures (3-6) and [structure(1-3)] reflected that the SNT acted as a

neutral N,N- bidentate ligand chelating via

nitrogenatomin(N=N)andnitrogenin(C=N)_imd.toformhexagonalchelatingring. This manner of

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chelation was rein forced by the change in shap and shift to lower wavenumberofbothʋ(N=N),ʋ(C-N=N-C)andʋ(C=N)andthepresenceofnewbands at (611-615) cm^-1 and (509-522)cm^-1which related to (M-Nimd.) and (M- Nazo)respectively[26].

Moreoverabrodningbandat(3385-3448)cm^-1inthespectra of the complexes[Pt(SNT)2Cl₂]Cl₂.H₂O,[Pd(SNT)2]Cl₂.H₂O due to the presence of lacttice or coordinated water. Generally, lattice water absorb at (3500-3200) cm^-1 (symmetricandasymmetricʋ (OH))[27]. This corresponds to the thermal analysis (TGA) and elemental analysis (C.H.N.S).

Furthermore,inthespectraofallcomplexesthedoubletbandsobserved at(1595- 1548)cm^-1duetotheʋ(c=o)pyrmandʋ(NH)pyrmtheyremainsmoreorless at the same position in complexation indicating that they are not a center of chelation.

Finally, the new band at (358-381) cm^-1 in the complex spectra related to ʋ(M-Cl)[28].

Structure (2)

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Structure (3)

Structure (4)

Table (4) Main spectroscopic FT – IR date for the ligand ( SNT) and its complexes

Assessme nt Center ʋ(O- H)H2O ʋ(N-H)NH Pyrm. δ(N-H) ʋ(C=N)Im d. ʋ(C=C)na ph. ʋ(C=O)Pyi m ʋ(C=O)ald . ʋ(N=N) ʋ(-C- N=N-C-) ʋ(S+aS SO3H) ʋ(M- N)Imd. ʋ(M-N)azo ʋ(M-Cl) ʋ(M- O)H2O

SNT -- 3458 m

1595 w

1595 d,m 1550 d,m

1695 d 1670

s ---

1485 T,s 1456

T,s 1432

T,s

1397 s

1226 d,s

1145 d,s --- --- --- H₂O

[Ni( SNT)2Cl2]

---

3398 s 1575

w

1575 d 1550

w

1714 d 1652

s ---

1438 w

1396 d,w 1367 d,s

1218 d,s

1176 d,s 613 m 516 w

337 s --

[Cu(SNT)₂Cl₂]

---

3432 m 1595

v.w

1595 d 1550

m

1693 s ---

1458 d 1434

w

1365 w

1222 d,s 1188

d,s

615 m 514 m

370 w

---

[Pd(SNT )2]Cl2

.H₂O 3415

br,m

3449 s 1598

w

1595 d,m 1560 d,m

1708 s ---

1458 d,w 1433

d,w

1404 d,w 1379

d,w

1226 T,s 1203

T,s 1176

T,s

613 m 522 w

358 s

---

[Pt(SNT )2Cl2]Cl2

.H2O 3448 br.

v.w

3440 v.w 1595

v.w

1595 d 1550

m

1691 s ---

1452 d,w 1423

d,w

1365 v.w

1224 d,m 1205 d,m

611m 511 w

368 w ---

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Figure (2): FTIR spectrum of SNT ligand.

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7-:1H-NMR

The ¹H-NMR studies are an additional support for the result obtained from the FT-IR spectra. Is achieved by considering the changes in the ¹H-NMR spectraof the synthesized complexes in comparison with the free ligand. The chemical shift data (𝛿 ) in ppm for different types of protons in the ligands (SNT) and their complexesforpd(II)andpt(IV)arereportedinTable(5)whiletheHNMRspectra were recorded in DMSO-d⁶ solution[Figure(7-9)].

The free ligand (SNT) display two singlet signals in the low field of TMS at (11.08and 8.71) ppm can be attributed to the protons of (NH)prm and (SO3H) respectively [29]. The multiplet signals detected in the range (7.10-8.06) ppm are referred to the naphthyl and phenyl ring in the ligand (SNT)[30]

In the spectra of Pd (II) and Pt (IV) complexes all signals have a light change, reflecting the non-involvement of these groups in coordination with metal ion and also, supporting the involvement of (N_azo)and (N_imd) in the coordination with Pd(II) and Pt(IV).

Table (5): ¹HNMR signals of SNT and their Complexes.

Compound NHPyim COHald. SO3H Harm. N-CH3 Imd. N-CH3Pyrm Ar-CH3 H2O

SNT 11.08 - 8.71 7.48-7.39 3.8

7

3.3

7 - - [Pd(SNT )₂] Cl₂.H₂O 11.08 - 8.82 8.30-7.86 3.8

1

3.4

7 - 3.3

4 [Pt(SNT )₂Cl₂]Cl₂

.H2O 11.08 - 8.91 7.99-7.86 3.8

7

3.3

6 - 3.2

8

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Magnetic properties and Electronicspectrum

The Electronic spectrum for the ligand (SNT) and its complexes were measured in ethanol (10⁻⁴M) (against ethanol as reference ) within the range (200-1100)nm.

The numerical date were listed in Table (6) and the electronic spectra were shown in Figures (10-14) .

The high bathochromic shift of 𝜆max proposed the involvement of the ligand in the chelation with the metal ion [Ni(п), pd(п) , pt (IV)and Cu(п)] , while appeared in the area of low wave length the peaks due to(d-d) transition.

The ligand (SNT) displays mainly three peaks. The first and two peaks at (242nm,,41322𝑚⁻¹) , ( 382nm ,26178c𝑚⁻¹), were assigned to the moderate energy (𝜋 − 𝜋*) transition of the aromatic naphthalene and pyrimidine ring , while the third peaks at(512nm,19531c𝑚⁻¹) was related to the n→ 𝜋* intermolecular transition charg transfer takingplace through the azo group and carbonyl group [31]

The spectrum of [Ni(SNT)2 Cl2]] complexes was shown three transitions Figure (11) 𝜐₁ =³A₂g_(F)→³T₂g _(F) at ( 919nm,10881cm⁻¹ )and 892nm, 11210cm⁻¹)

𝜐₂= ³A2g (F)→³T2g (F) at (889nm,1124 cm⁻¹ ) 𝜐₃= ³A2g (F)→³T2g (F) at(520nm,19230c𝑚⁻¹)

These transition are characteristic for octahedral Ni(п) 𝑑⁸ complex Moreover the magnitude of magnetic moment (2.9) B.M which consist with octahedral configuration high spin [32].

As for the band belonging to metal to ligand charge transfer (MLCT) nested with(𝜐₃).

In the spectrum of the low spin(d⁸) pd(п) - complexes [Figers (12 )], the peak was related to the ligand (SNT ) which was shifted ,as expected to red shift by (14nm ) The Three (d-d) transitions were predicted for square planar (d⁸)¹A₁g → ¹A₂g,¹A₁g →¹B₁g and

1A₁g →¹E₁g [33] Only two transtions were obseved at (916nm, 10917c𝑚⁻¹),[(966nm,10905c𝑚⁻¹) for pd(SNT)₂] Cl₂.H₂O which belonge to ¹A₁g¹→¹B₁g and ¹A1g → ¹A2g, receptively while the transitions ¹A1g¹→¹E1g may be hiddin by the (M LCT) band at (556nm,17985c𝑚⁻¹) for so the magnetic moment is zero and diamagnetic .

The electronic spectrum of high spin pt (IV) complex was showed a red shift of the π → π* transition for the ligand SNT from (512nm,cm⁻¹) to(666nm , cm⁻¹) as was shown in Figure (13) There are three (d-d) transitions were expected for Pt(IV) -complexes (d⁶), octahedral with diamagnetic properties in the visible region [34]

3A₂g→¹T₁g

3A₂g→¹T₂g

3A2g→³T3g(forbiden transition)

All transition were included in Table (6) for the synthesized pt(IV) –complex with diamagnetic properties.

Finally The magnetic moment value of the synthesized Cu(II) – complex (1.86B.M) lie within the range of Cu (II)d⁹ (ion The electronic spectrum of [Cu (SNT)₂Cl₂] appeared abroad band at (616m,16233c𝑚⁻¹) which related to ²B1g →²Eg and ²B1g →²B2g, in a tetragonally distorted octahedral (D4h) [35].

Figure (9)

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Fig.(10) : UV-Vis Spectrum for the SNT.

Fig. (11) : UV-Vis Spectrum for the Ni(II)-SNT.

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Fig.(12): UV-Vis Spectrum for the Pd(II)-SNT.

Fig.(13): UV-Vis Spectrum for the Pt(IV)-SNT.

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Fig. (14) : UV-Vis Spectrum for the Cu (II) - SNT .

Table(6): Electronic transition, hybridization and geometry at the ligand and their complex's at (𝟏𝟎^−𝟒M)

Compound ℷ(𝒏𝒎) Wavenumber (c𝒎^−𝟏)

Assignment hybridizati on

Geometry

SNT 242

362 512

41322 27624 19531

π → π*

n → π*

π → π*

_____ _____

[Ni(SNT)2Cl2] 242 366 520 889 919

41322 27322 19230 11248 10881

π → π*

n → π*

3A₂g_(F)→³T₂g_(p)

3A2g(F)→³T2g(F) 3A2g(F)→ T1g(F)

Sp³d² octahedral

[Pd(SNT)₂] Cl2.H2O

298 556 916 966

33557 17985 10917 10351

π → π*

MLCT

1B₁g→¹A₁g

1A1g→¹T2g

Sp³d Square planer

[Pt(SNT)2d2] Cl2.H2O

242 416 516 666 917 976

41332 24038 19379 15015 10905 10245

π → π*

n → π*

MLCT

1A1g→¹T1g

1A₁g→¹T₂g

1A₁g→³T₁g

d² Sp³ octahedral

[Cu(SNT)2Cl2] 242 362 616

41322 27624 16233

π → π*

n → π*

2B1g→²Eg+2

B1g→²B2g

Sp³d² Tetragonal

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8-Thermo gravimetric Analysis (TGA) and Differential scanning colorimetry (DSC) The Thermo gravimetric analysis has a major role in assessing the properties for the compounds aside from stoichiometry for the dented volatile decomposition products. The investigated ligand (SNT) and its complexes were suspected, in argon flow within the temperature range (25 – 1000) C^o The number of stages, stages of degradation, the calculated and the obtained weight loss percentages, degradation product loss and the residues are listed in Table (7) and represented graphically in Figures [(15-19)]

The results were showed that the ligand and its complexes were decomposed in (3-5) steps with exothermic effect in DSC curve . The hydrated water molecule were volatilize within temperature rang (25-200)C^o, . All complexes were displayed the decomposition of the organic ligand within the range (200 – 1000) C^o leading to metal oxid as residue. As well As from Table (7) we conclude the following :

1- The thermal stability of the new compounds are :

[pd (SNT)2 ] Cl2 .H2O˃𝑆𝑁𝑇˃[𝑃𝑡(SNT)2 ] Cl2 .H2O˃[Cu (SNT)2 Cl2]˃ Ni (SNT)2 Cl2

2- The results are showed in good agreement with the formula suggested from analytical results .

Table (7): (TGA) and (DSC) of ligand (SNT ) and its complexes

Com. Sym.

Molecular formula(molecular

weight) g/mole

Step

TG. Range of the decomposition

(℃)

Suggested Assignment

Mass loss %

DSC

℃ Calcula

te

%

Found

%

SNT C17H14N6O5S)

(414.404)

1 25-230 C^o Hcl C₂ H₂ 6.48

6.50

230.5 9 EXO 2 230-575 C^o C₃₂ H₂₅ CL N₁₂ S2

O₄ 76.89 77.07

318.3 8 EXO

3 575-1000 C^o 15.90 15.70

Residue 0.65 <1000

C^o

[Ni( SNT )₂Cl₂]

NiC34H28N12O10S2Cl 2

(958.498)

1 25-455 C^o C34H28N12Cl2S

2O7 88.78 89.02

345.7 2 EXO

2 455-1000 C^o Ni0.89O3 10.45 10.3

3

Residue 0.11Ni 0.67 0.68

[Cu(SNT )₂Cl₂] CuC34H30N12O11S2Cl 2

(963.348)

1 25-230 C^o C5H3 6.54 6.5

208.7 7 EXO 2 230-565 C^o C29H25Cl2N12S

2O45 77.72 77.07

331.3 4 EXO 3 565-1000 C^o 0.88CuO6.5 16.61 15.70

619.7 0 EXO

Residue 0.12Cu 0.79 0.73

[Pd(SNT )2]Cl2 .H2O

PdC34H30N12O11S2Cl

1 25-160 C^o H₁₄O 2.92 2.82 95.93

EXO 2 160-490 C^o C₃₄ H₆ Cl₂ N₅ 54.18 54.26 327.9

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4 (1024.228)

3 EXO 3 490-1000 C^o H10 N6 S2 15.42 15.71

Residue Pd O₁₀ N 27.37 27.21

[Pt(SNT)₂Cl₂]Cl₂

.H₂O PtC34H30N12O11S2Cl4 (1083.892)

1 25-125 C^o H₉O 2.11 2.14

2 125-400 C^o C₃₄ H₂₁ Cl₄ 48.23 48.39

333.6 3 EXO

3 400-570 C^o N₅ S₂ 11.31 11.05

431.3 2 EXO

4 570-750 C^o N6 7.09 7.01

681.1 4 EXO

5 750-1000 C^o NO₇ 10.64 10.67

812.6 5 EXO Residue >1000 C^o PtO₄ 21.81 20.73

Figure (15): DSC-TGA for the (SNT) of the ligand

(19)

Figure (16): DSC-TGA for the [Ni( SNT )₂Cl₂] Complex

Figure (17): DSC-TGA for the [Cu(SNT )2Cl2] Complex

Figure (18): DSC-TGA for the [Pd (SNT )2] Cl2 .H2O Complex

(20)

Figure (19): DSC-TGA for the [Pt(SNT )2Cl2]Cl2 .H2O Complex 9-Scanning Electron microscopy Analysis (SEM)

the topographical surface of different samples shows the micro structures of these surfaces . the electrons were interested with the atoms in the sample , producing various signds that contain information about the topography and composition of the surface [36]

The morphology for the ligand (SNT) with their complexes was appeared different crystal line structures and surface homogeneities. An accreditation was done in SEM technique on area of a cross section (100nm) and enlarging power (Mag=60.00KX) as was shown in Figure [(20-24)]. The SEM images explained heterogeneous surfaces with different shapes soit varies with different compound and difference volume for paricale [Table](11).

Table(11).SEM date for the ligand(SNT) and its complexes

Compound Average volume (nm) shape

SNT

[Ni(SNT)₂Cl₂] [Pd(SNT)2] Cl2.H2O [Pt(SNT)2d2] Cl2.H2O [Cu(SNT)₂Cl₂]

231.64 100.56 348.24 170.06 103.11

Cubic Coral

Different shape Different shape Spherical

(21)

(20) SEM for [SNT]

(21) SEM for [Ni(SNT)

₂

cl

₂

]

(22)

(22) SEM for [Cu(SNT)

₂

cl

₂

]

(23)

10-Antibactiralof ‎the SNTand their metal complexes

supervision of microbial population is important to prohibit show of infection, disease, ‎ damage and contamination caused by them. The novel azo ligand (SNT)‎ and its complexes were screened for antimicrobial efficiency in vitro with four ‎pathogenic microorganisms by disk diffusion process [37]. The microorganisms utilized were of ‎ Pathogenic nature and have been specified to cause much life –threatening diseases in ‎living system. They were two gram –negative bacteria species (E.coli and Klebsiella) and to ‎gram-

‎positive bacteria species (Streptococcus and Staphylococcus). All obtained results are ‎ reported in Table (9) and represented in Figure (25). From the results obtained, ‎all of the tested compounds have moderate to strong efficiency except nickel (II)‎complexes , has been

‎showed no efficiency with all type of selected bacteria their where compared withAmoxicillin as a reference antibacterial and appeared good inhibition to the same ‎ pathogenic bacteria .‎Through the obtained result, its concluded that the synthesized compounds may be ‎integrated into DNA helix chains in bacteria molecules , which are available to damage theMicroorganism’s biological methods . On the other hand the coordination bonds ‎between ‎the azo ligand (SNT) and selected metal ions may enhance the efficiency with various bacteria species due to the overtone concept of cell permeability protein that ‎the ‎ cell is enclosed with a lipid membrane, which favors the passing only lipid soluble ‎materials[38] . In coordination the positive charge of metal ion is partially shared with ligand ‎donor atom, and thus there is electron delocalization over the whole coordination ring. ‎ So , the lipophilicity of the compounds are increased . The penetration of the metal ‎ions complexes in to lipid membrane will increase, which owing to blocking of the metal ‎binding sites on enzymes for microorganisms. Moreover, the formation of bacterial cell wall ‎be ruptured, they will perish and the growth of the organism will be stop.

Finally, these compounds also destroy the respiration process of the cell, which leads to not synthesis ‎of ‎proteins [39]. ‎

Table (12): The inhibition zones scale in (mm) of Amoxicillin, ligand (SNT) and its complexes

Compounds.000000

Gram Negative Gram Positive Escherichia

coli

klebsiell a

streptoco ccus

Staphylococc us

(24)

Amoxicillin 15 10 12 14

1 SNT 10 10 10 10

2 ‎[Ni(SNT)2Cl2]‎ 0 0 0 0

3 ‎[Cu(SNT)2Cl₂]‎ 0 10 0 0

4 ‎[Pd(SNT)2]Cl₂ .H₂O 10 15 16 15

5 ‎[Pt(SNT)2Cl₂]Cl₂.H₂O ‎ 10 0 10 10

Figure (25): The inhibition zone for SNT and its complexes 11-The Cytotoxic Effecrs

Since the find out of cisplatin , many new pt and pdcomplexes have been synthesized and estimated for their cytotoxic activity Although there are different drugs for the treating carcinoma, still it remains the main cause of death worldwide because of limitations such as multidrug resistance.high toxicity and adverse side effects [40] therefore, they have been many defrosts to find compounds which is might serve as more effective less toxic and adverse side effects anticaranoma drugs [41].Thus , recent studies have been converged on the synthesizing of effective compounds having heterocyclic ring aschemotherapeutic drugs [42]. And well to define the performance of any now compound that can be utilized as anticaranoma drugs it is necessary to define how it improves clinical land hematological

(klebsiella) (E-Coli)

(Streptococc)

(Staphylococcus

‎).

(25)

fastors, the biochemical profile and reduces fertile tumor call counting in the host and also prolongs the life span [43].

In this divection, we have investigated the cytotoxic activity and mechanism of action for the synthesized (SNT) ligand with its (𝑃𝑑(II))and pt(III) complexes against lung carcinoma cell line (A549) and normal cell line (WRL68) by MTT assay after incubated for 24hr and 72hr at 37C° and with concentrations (10,20,30,50,100) 𝜇𝑔/ml.It was found that the selected compounds had various growth inhibitory effects on A549 and WRL68 cell line the extetent at toxic effect was estimated by measuring the percentage of cell growth inhibition compared to the control. the results from Table 13 − 15 andFigures (26-28) .were shown that, after incubation at concentration (10-100) 𝜇𝑔 /ml of the(SNT), and selected complexes for 24 hrs and 72 hrs with A549 and WRL68 cells line ,a series of morphological modifications for DNA inclusive condensation fragmentation of chromatin and nucleus with formation of opoptotic bodies were observed which was the proof of apoptosis and drug potential of the tested compound [44].

Table (13) Evolution at cytotoxicity of the ligand (SNT) against A549 censer cell line and WRL – 68 cell line after incubation for (24 hours) at (37)℃

p- value IC 50

Mg/ml Number

of values Concentration (Mg/ml)

Cell line

100 50

30 20

10

<0.000 1 49.22

70.988 3

∓ 1.275 81.983

∓ 0.372 94.637

∓1.802 94.560

∓ 0.759 95.062

∓ 1.341 A₅₄₉

52.12 76.968 3

∓ 1.446 86.729

∓ 1.205 93.982

∓ 2.729 94.599

∓ 0.735 94.599

∓ 0.291 WRL-

68

After incubation for (72 hours) at (37)℃

p- value IC 50

Mg/ml Number

of values Concentration (Mg/ml)

Cell line

100 50

30 20

10

<0.000 1 26.50

39.429 3

∓ 2.793 52.122

∓ 3.848 61.381

∓ 1.275 83.457

∓2.039 95.949

∓ 0.909 A549

65.4 59.221 3

∓0.965 73.611

∓ 2.523 79.707

∓ 1.753 83.873

∓ 1.718 82.986

∓ 0.504 WRL-

68

(26)

Figure (26)cytotoxicity effect of (SNT)on A

549

cancer cell line and WRL-68

cell line after incubation (24and72hours)

(27)

Table (14) Evaluation of cytotoxicity of [pt(SNT)

2

Cl

2

]Cl

2

.H

2

O against A

549

cancer cell line after incubation (24 hours) at (37C

^o

) and WRL-68 cell line p- value IC 50

Mg/

ml Number

of values Concentration (Mg/ml)

Cell

line 10 20 30 50 100

<0.00 1 28.2

59.915 3

∓ 3.323 63.696

∓ 2.123 75.309

∓ 4.148 88.272

∓ 2.568 94.792

∓ 1.335 A

549

38.17 65.702 3

∓ .654 74.460

∓ 0.854 87.114

∓ 3.649 96.180

∓1.252 96.952

∓ 1.142 WRL-

68 After incubation (72 hours) at (37C

^o

)

p- value IC 50

Mg/

ml Number

of values Concentration (Mg/ml)

Cell

line 10 20 30 50 100

<0.00 1 22.62 49.383 3

∓3.021 49.961

∓2.135 59.529

∓ 1.226 71.026

∓ 1.075 84.144

∓ 0.810 A

549

43.14 51.119 3

∓2.100 63.195

∓2.652 74.306

∓ 5.171 82.986

∓ 1.422 83.642

∓0.821 WRL-

68

(28)

Figure (27) cytotoxicity effect of [pt(SNT)₂Cl₂]Cl₂.H₂O on A₅₄₉ cancer cell line and WRL-68 cell line after incubation (24 and 72 hours)

(29)

Table (15) Evaluation of cytotoxicity of [pd(SNT)

2

Cl

2

]Cl

2

.H

2

O against A

549

cancer cell line after incubation (24 hours) at (37C

^o

) and WRL-68 cell line p- value IC 50

Mg/

ml Number

of values Concentration (Mg/ml)

Cell

line 10 20 30 50 100

<0.00 1 20.00 3

39.043 ∓ 3.773 43.634

∓ 2.349 50.000

∓ 1.335 59.568

∓ 0.821 72.801

∓0.904 A

₅₄₉

37.19 3

64.622 ∓ 1.969 73.225

∓ 1.205 84.336

∓ 2.663 94.946

∓ 0.998 94.830

∓0.971 WRL-

68 After incubation (72 hours) at (37C

^o

) and WRL-68 cell line

p- value IC 50

Mg/

ml Number

of values Concentration (Mg/ml)

Cell

line 10 20 30 50 100

<0.00 1 23.27 3

25.617 ∓ 1.301 30.710

∓ 1.270 37.384

∓ 3.457 51.235

∓ 2.956 63.233

∓ 1.395 A

₅₄₉

52.48 3

50.424 ∓ 5.366 660127

∓ 2.445 74.460

∓ 5.595 84.143

∓ 0.644 83.835

∓ 1.142 WRL-

68

(30)

Figure(28) cytotoxicity effect of [pd(SNT)₂Cl₂]Cl₂.H₂O on A₅₄₉ cancer cell line and WRL- 68 cell line after incubation (24 and 72 hours)

(31)

12-Dying performance

The quality of any fabric is directly attached on the quality of the fabric utilized to manufacture the product. More maximize dyeing procedure capacity and color performance properties [45]. The fabric fibers involved must be as clean as possible . The main target of preparation is the elimination of both naturally occurring impurities and those which are added during yarn or textile manufacturing [46]. the dying opration can be perfected on textile fabrics , yarns fabrics or garments according to the properties or for cost control .Dyes are the chemicals that are absorbed into the molecular structure of fibricfibris , which produce the color of. The molecular structure of fibric fibers. As well As is the opration which places the dyes inside the fibric fibers. the dyeing tools is used to control the necessary parameters of the dying opration in order to maximized dyeing productivity and quality [47] .

In our research cotton fabries were used for dyeing the ligand (SNT) and its complexes. The color of cotton fabrics after dying with these compound were ranged between yellow , pink ,green . As the azo compounds are considered effective dyes , which contain one or two groups that have the ability to bonded with the oxegen atom of hydroxyl group in cellulose which is the main component of cotton and all dyeing processes from

bleaching and dying. Structure of Cellulose [48]

In order to know the most important properties of the synthesized dyes, investigative studies were conducted as follows :

wash fastness

The wash fasness of synthesized ligand (SNT ) and its complexes were examined depending on the (ISOO IOS CC6C25) With standard soup (SDC) [49] .

The results we a btained for all compounds were excellent. As previously mentioned because of the presence of many active groups in the composition of the compounds which helps the strength of the bonded between the dye and cotton fabrics cellulose .

Thermal stability

As Previously mentioned thermal stability has beestudied represented TGA and DSC . All the synthesized compounds have high stability in high temperature .

Photo stability

The photo stability study of the ligand (SNT) and its complexes was carried out by taking an ethanolic solution of them in a concentration (10^-4M) and irradiation them with (UV) rays for period (2hours) at room temperature all results were collected in Table( 17) and the photo stability was calculated as the ratio to difference between the initial absorbance. i.e.

before irradiation and the final, to the intial absorbance The coalition was follow [Cu(SNT)2Cl2]>[Ni (SNT)2Cl2] > [Pd(SNT)2]Cl2 .H2O > [Pt(SNT)2Cl2]Cl2. H2O]>SNT

(32)

Table (17) photo degradation details of ligand and its complexes under irradiation (𝝀

=256 nm, power = 250w)

Com pound Time

(sec)

Abs (nm)

Photo –

stability percent

SNT 0 3.974 1.48%

10 3.919

30 4.000

60 3.914

120 3.915

‎[Ni(SNT)2Cl2]‎ 0 3.979 5.60%

10 3.900

30 3.938

60 3.960

120 3.756

‎[Pd(SNT)2]Cl₂ .H₂O 0 3.985 3.98%

10 3.973

30 9.953

60 3.977

120 3.826

‎[Cu(SNT)2Cl2]‎ 0 0.625 7.22%

10 0.603

30 0.597

60 0.588

120 0.578

‎[Pt(SNT)2Cl2]Cl2.H2O ‎ 0 0.627 3.703

10 0.621

30 0.620

(33)

60 0.616

120 0.604

13-Conclusion

Ni(II) pd (II), pt ( IV) and Cu (II) complexes of (SNT) ligand were synthesized . It was performed asN,N-bidentate coordinates. The geometry of Ni (II) and pt (IV) complexes are assumed octahedral while pd (II) complexes has square planar geometry and Cu (II) complexes has distorted octahedral geometry based on the available data from the spectroscopy has (FT - IR, UV –Vis, HNMR) Spectra, elemental analysis, molar conductivity, magnetic susceptibility, TGA, DSC and SEM The antibacterial, anticancer assay and dye performance were investigated .

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